Metallocenes, process for their preparation and their use as catalysts

ABSTRACT

The present invention relates to a polynuclear metallocene compound of the formula I ##STR1## a process for their preparation and their use as a catalyst for olefin polymerization.

The present invention relates to novel metallocenes which contain morethan one central atom and can be advantageously used as catalystcomponents in the preparation of polyolefins, in particular those havinghigh stereo-regularity, high molecular weight and good grain morphology.

The preparation of polyolefins using soluble metallocene compounds incombination with aluminoxanes or other cocatalysts, which owing to theirLewis acidity can convert the neutral metallocene into a cation andstabilize it, is known from the literature.

Soluble metallocene compounds based on bis(cyclopentadienyl)zirconiumdialkyl or dihalide in combination with oligomeric aluminoxanes havegood activity in polymerizing ethylene and moderate activity inpolymerizing propylene. The polyethylene obtained has a narrow molecularweight distribution and intermediate molecular weight. The polypropyleneprepared in this way is atactic and has a very low molecular weight.

The preparation of isotactic polypropylene can be successfully carriedout using ethylenebis(4,5,6,7-tetra-hydro-1-indenyl)zirconium dichloridetogether with an aluminoxane in a suspension polymerization (EP 185918). The polymer has a narrow molecular weight distribution. Thedisadvantage of this process is that at industrially applicablepolymerization temperatures, only polymers having a very low molecularweight can be prepared.

There has also been described a specific preactivation method for themetallocene using an aluminoxane, which leads to an appreciable increasein the activity of the catalyst system and to a significant improvementin the grain morphology of the polymer (EP 302 424). However, thepreactivation does not significantly increase the molecular weight.

Furthermore, catalysts based on ethylenebisindenylhafnium dichloride andethylenebis(4,5,6,7-tetrahydro-1-indenyl)-hafnium dichloride andmethylaluminoxane are known, by means of which relativelyhigh-molecular-weight polypropylenes can be prepared by suspensionpolymerization (J. Am. Chem. Soc.(1987), 109, 6544). However, underindustrially applicable polymerization conditions, the grain morphologyof the polymers produced in this way is not satisfactory and theactivity of the catalyst systems used is comparatively low. Furthermore,these systems have high catalyst costs, so that low-cost polymerizationis not possible using these systems.

A significant increase in the molecular weight could be achieved by theuse of metallocenes in which the indenyl ligands fixed by means of abridge bear substituents in the 2 position (EP 485 822) or in the 2 and4 positions (EP 530 647).

A further increase in the molecular weight was achieved by the use ofindenyl ligands having substituents in the 2, 4 and 6 positions (EP 545303) and also aromatic π ligands of the 4,5-benzoindenyl type (EP 549900).

A disadvantage in the case of the stereospecific polymerization ofprochiral monomers, e.g. of propylene, using metallocene catalysts isthe relatively low isotacticity, which in the case of isotacticpoly-propylene results in low melting points. Metallocenes havingsubstituents in the 2 and 4 positions in particular and specificallyrac-dimethylsilylbis(2-methyl-4-isopropylindenyl)zirconium dichloride incombination with methylaluminoxane give, in the case of propylene, apolymer having high isotacticity and therefore a high melting point (EP530 647). A further increase in the melting points was achieved by theuse of 4-aryl-substituted bisindenyl systems (EP 576 970).

However, there are also industrial applications in which low meltingpoints are desired.

A disadvantage of the use of soluble (homogeneous)metallocene-methylaluminoxane catalyst systems in processes in which thepolymer is obtained as a solid, is the formation of heavy deposits onreactor walls and stirrers. These deposits are formed by agglomerationof the polymer particles if the metallocene or aluminoxane or both arepresent in solution in the suspension medium. Such deposits in thereactor systems have to be removed regularly, since these quickly reachconsiderable thicknesses, have a high strength and prevent heat exchangeto the cooling medium.

To avoid reactor deposits, metallocenes can be supported. Processes forthis purpose are known (EP 578 838). For technical reasons, it would beadvantageous to omit the additional process step of supporting thecatalyst. EP 528 041 discloses binuclear metallocenes which are suitablefor the preparation of syndiotactic polymers having a low molecularweight.

It is an object of the invention to avoid the disadvantages of the priorart, and particularly to find a catalyst system which gives high yieldsof polymers having a very high molecular weight and, in the case of thestereo-specific polymerization of prochiral monomers, polymers havinghigh stereoregularity.

It has now been found that metallocenes which contain more than onecentral atom and have a special bridge structure are suitable catalystswhich avoid the dis-advantages known from the prior art. Surprisingly,it has been further found that the metallocenes of the invention areparticularly suitable for preparing isotactic polyolefins having only alow proportion of extractable material.

The present invention accordingly provides a polynuclear metallocenecompound of the formula I ##STR2## where M¹ are identical or differentand are a metal of group IVb, Vb or VIb of the Periodic Table,

X are identical or different and are hydrogen, a C₁ -C₁₀ -alkyl group, aC₆ -C₁₀ -alkoxy group, a C₆ -C₁₀ -aryl group, a C₆ -C₁₀ -aryloxy group,a C₂ -C₁₀ -alkenyl group, a C₇ -C₄₀ -arylalkyl group, a C₇ -C₄₀-alkylaryl group, a C₈ -C₄₀ -aryl-alkenyl group, an OH group, a halogenatom or pseudohalogen,

L and L' are identical or different and are π ligand or another electrondonor,

k is 2 if B is ##STR3## and k is an integer ≧2 if B is ##STR4## where R¹are identical or different and are a divalent hydrocarbon-containingbridge structure,

the radicals R² are identical or different and are a hydrogen atom, ahalogen atom or a hydrocarbon-containing radical,

R³ is a trivalent hydrocarbon-containing radical, and n is k and m isk-1 and

M² is silicon, germanium or tin.

For the purposes of clarity, it should be pointed out that each "free"valence of the structural elements B links to a ligand L or L'.

M¹ are identical or different and are a metal of the group IVb, Vb orVIb of the Periodic Table, for example titanium, zirconium, hafnium,vanadium, niobium, tantalum, chromium, molybdenum or tungsten,preferably zirconium, hafnium and titanium.

The radicals X are identical or different and are a hydrogen atom, a C₁-C₁₀ -, preferably C₁ -C₄ -alkyl group, a C₁ -C₁₀ -, preferably C₁ -C₃-alkoxy group, a C₆ -C₁₀ -, preferably C₆ -C₈ -aryl group, a C₆ -C₁₀ -,preferably C₆ -C₈ -aryloxy group, a C₂ -C₁₀ -, preferably C₂ -C₄-alkenyl group, a C₇ -C₄₀ -, preferably C₇ -C₁₀ -arylalkyl group, a C₇-C₄₀ -, preferably C₇ -C₁₂ -alkylaryl group, a C₈ -C₄₀ -, preferably C₈-C₁₂ -arylalkenyl group, or a halogen atom, preferably chlorine or apseudohalgen like nitrile.

L and L' are identical or different and are preferably a substituted orunsubstituted cyclopentadienyl group, O, S, PR⁴ or NR⁴, where R⁴ is ahydrogen atom or a C₁ -C₃₀ -hydrocarbon radical such as C₁ -C₂₀ -alkylor C₆ -C₁₄ -aryl.

Examples of L and L' are: tert-butylamido, cyclohexylamido, phenylamido,2,6-di-isopropylphenylamido, 2,6-ditert-butylphenylamido,cyclododecylamido, cyclopentadienyl, tetramethylcyclopentadienyl,methylcyclopentadienyl, methyl-tert-butylcyclopentadienyl,tert-butylcyclopenta-dienyl, isopropylcyclopentadienyl,dimethylcyclopentadienyl, trimethylcyclopentadienyl,trimethylethylcyclopentadienyl, phenylcyclopentadienyl,diphenylcyclopentadienyl, indenyl, 2-methylindenyl, 2-ethylindenyl,3-methylindenyl, 3-tert-butylindenyl, 3-trimethylsilylindenyl,2-methyl-4-phenylindenyl, 2-ethyl-4-phenylindenyl,2-methyl-4-naphthylindenyl, 2-methyl-4-isopropylindenyl,4,5-benzoindenyl, 2-methyl-4,5-benzoindenyl,2-methyl-α-acenaphthindenyl, 2-methyl-4,6-diisopropyl-indenyl,fluorenyl, 4-methylfluorenyl or 2,7-di-tert-butylfluorenyl.

B is ##STR5## where R¹ are identical or different and are a divalenthydrocarbon-containing C₁ -C₄₀ bridge structure, preferably a divalentC₁ -C₄₀ -alkyl group, C₁ -C₁₀ -fluoroalkyl group, C₆ -C₁₀ -aryl group,C₆ -C₁₀ -fluoroaryl group, C₇ -C₂₀ -alkylaryl group, C₇ -C₂₀ -arylalkylgroup, C₁ -C₁₀ -alkoxy group, C₆ -C₁₀ -aryloxy group, C₂ -C₁₀ -alkenylgroup or C₈ -C₂₀ -arylalkenyl group,

the radicals R² are identical or different and are a hydrogen atom, ahalogen atom, or a hydrocarbon-containing C₁ -C₄₀ radical such as a C₁-C₁₀ -alkyl group, a C₁ -C₁₀ -fluoroalkyl group, a C₁ -C₁₀ -alkoxygroup, a C₆ -C₁₀ -aryl group, a C₆ -C₁₀ -fluoroaryl group, a C₆ -C₁₀-aryloxy group, a C₂ -C₁₀ -alkenyl group, a C₇ -C₂₀ -alkylaryl group, aC₇ -C₄₀ -alkylaryl group or a C₈ -C₄₀ -arylalkenyl group and R³ is atrivalent hydrocarbon-containing C₁ -C₄₀ radical, preferably a C₁ -C₄₀-hydrocarbon radical, particularly preferably a trivalent C₇ -C₄₀ -alkylgroup, C₁ -C₄₀ -alkylaryl group, C₆ -C₄₀ -arylalkyl group, C₂ -C₄₀-alkenyl group or C₇ -C₄₀ -arylalkenyl group, n is k and m is k-1 and M²is silicon, germanium or tin.

If B is ##STR6## k is preferably an integer from 2 to 100,000,particularly preferably from 2 to 20, in particular 2.

Preferably, B is ##STR7## where the radicals R¹ are identical ordifferent and are a divalent C₁ -C₁₀ -, preferably C₁ -C₆ -alkyl groupwhich can be linear or branched, in particular 1,2-ethanediyl,1,3-propanediyl, 1,4-butanediyl, 1,6-hexanediyl, ethylene,1,3-propylene, 1,4-butylene, 1,6-hexylene, a C₆ -C₁₀ -, preferably C₆-aryl group, in particular 1,4-phenylene, a C₆ -C₁₀ -fluoroaryl,preferably C₆ -fluoroaryl group, a C₇ -C₂₀ -alkylaryl, preferably C₇-C₁₂ -alkyl-aryl group, in particular p-xylylene, m-xylylene,o-xylylene, a C₇ -C₂₀ -arylalkyl, preferably C₇ -C₁₂ -arylalkyl group, aC₁ -C₁₀ -alkoxy, preferably C₁ -C₆ -alkoxy group, a C₂ -C₁₀ -alkenyl,preferably C₂ -C₆ -alkenyl group, a C₈ -C₂₀ -arylalkenyl, preferably C₈-C₁₄ -arylalkenyl group, the radicals R² are identical or different andare a hydrogen atom, a halogen atom, a C₁ -C₁₀ -, preferably C₁ -C₄-alkyl group, in particular a methyl group, a C₁ -C₁₀ -fluoroalkyl,preferably CF₃ group, a C₆ -C₂₀ -, preferably C₆ -C₁₀ -aryl group, a C₆-C₁₀ -fluoroaryl group, preferably a pentafluorophenyl group, a C₁ -C₁₀-, preferably C₁ -C₄ -alkoxy group, in particular a methoxy group, a C₂-C₁₀ -, preferably C₂ -C₄ -alkenyl group, a C₇ -C₄₀ -, preferably C₇-C₁₀ -arylalkyl group, a C₈ -C₄₀ -, preferably C₈ -C₁₂ -arylalkenylgroup, a C₇ -C₄₀ -, preferably C₇ -C₁₂ -alkylaryl group, and n is k andm is k-1, and

M² is silicon, germanium or tin, preferably silicon or germanium, inparticular silicon.

Preference is given to compounds of the formula II ##STR8## where M¹ areidentical or different and are a metal of group IVb, Vb or VIb of thePeriodic Table,

X are identical or different and are hydrogen, a C₁ -C₁₀ -alkyl group, aC₁ -C₁₀ -alkoxy group, a C₆ -C₁₀ -aryl group, a C₆ -C₁₀ -aryloxy group,a C₂ -C₁₀ -alkenyl group, a C₇ -C₄₀ -arylalkyl group, a C₇ -C₄₀-alkylaryl group, a C₈ -C₄₀ -aryl-alkenyl group, an OH group, a halogenatom or pseudo-halogen,

the radicals R⁵, R⁶, R⁷ and R⁸ are identical or different and are ahydrogen atom, a halogen atom, a C₁ -C₁₀ -alkyl group which can behalogenated, a C₆ -C₂₀ -aryl group, a C₇ -C₄₀ -arylalkyl group, a C₇-C₄₀ -alkylaryl group, a C₂ -C₁₀ -alkenyl group, a C₈ -C₄₀ -arylalkenylgroup, a --NR¹⁵ ₂, --SR¹⁵, --OSiR¹⁵ ₃, --SiR¹⁵ ₃ or --PR¹⁵ ₂ radical,where R¹⁵ is identical or different and is a C₁ -C₁₀ -alkyl group or aC₆ -C₁₀ -aryl group, or two or more adjacent radicals R⁵, R⁶, R⁷ and R⁸together with the atoms connecting them form a ring system,

R⁹ to R¹⁴ are identical or different and are a hydrogen atom, a halogenatom, a C₁ -C₁₀ -alkyl group which can be halogenated, a C₆ -C₂₀ -arylgroup, a C₇ -C₄₀ -arylalkyl group, a C₇ -C₄₀ -alkylaryl group, a C₂ -C₁₀-alkenyl group, a C₈ -C₄₀ -arylalkenyl group, a --NR¹⁵ ₂, --SR¹⁵,--OSIR¹⁵ ₃, --SiR¹⁵ ₃ or --PR¹⁵ ₂ radical, where R¹⁵ is identical ordifferent and is a C₁ -C₁₀ -alkyl group or a C₆ -C₁₀ -aryl group, or twoor more adjacent radicals R⁹, R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ together withthe atoms connecting them form a ring system,

k is 2, if B is ##STR9## and k is an integer ≧2, if B is ##STR10## whereR¹ are identical or different and are a divalent hydrocarbon-containingC₁ -C₄₀ bridge structure,

the radicals R² are identical or different and are a hydrogen atom, ahalogen atom or a hydrocarbon-containing C₁ -C₄₀ radical,

R³ is a trivalent hydrocarbon-containing C₁ -C₄₀ radical, and n is k andm is k-1 and

M² is silicon, germanium or tin.

For compounds of the formula II, it is particularly preferred that

M¹ are identical or different and are zirconium or hafnium,

the radicals X are identical and are a C₁ -C₄ -alkyl group, a C₇ -C₁₀-alkylaryl group or a halogen atom,

R⁵ to R⁸ are identical or different and are a hydrogen atom, a C₁ -C₁₀-alkyl group, a C₆ -C₂₀ -aryl group or a SiR¹⁵ ₃ radical where R¹⁵ is aC₁ -C₁₀ -alkyl group, or the radicals R⁵ and R⁶ and/or R⁷ and R⁸together with the atoms connecting them form an aromatic or aliphaticring system,

R⁹ to R¹⁴ are identical or different and are a hydrogen atom, a C₁ -C₁₀-alkyl group or a C₆ -C₂₀ -aryl group, or

R⁹ and R¹⁰ and/or two or more adjacent radicals R¹¹, R¹², R¹³ and R¹⁴together with the atoms connecting them form an aromatic or aliphaticring system,

k is 2.

B is ##STR11## where M² is silicon,

R¹ are identical or different and are a divalent linear or branched C₁-C₆ -alkyl group, in particular 1,2-ethylene, 1,3-propylene,1,4-butylene or 1,6-hexylene and

the radicals R² are identical or different and are hydrogen, a C₁ -C₄-alkyl group or a C₆ -C₁₀ -aryl group.

Isotactic polyolefins are preferably prepared using compounds of theformula II which have two indenyl groups as ligands. For this purpose,particular preference is given to compounds of the formula II in whichthe indenyl groups are substituted in the 2 position, 2,4 positions, 2,6positions, 2,4,6 positions, 2,4,5 positions, 2,4,5,6 positions and 2,5,6positions, with the 2 position preferably being substituted by a C₁ -C₁₀-alkyl radical and the 4, 5 and 6 positions being substituted by C₁ -C₁₀-alkyl radicals, C₆ -C₁ -aryl radicals or by fusion in the 4,5 or 4,5,6positions. The term ring system thus includes both substituted andunsubstituted ring systems.

The nomenclature used for the point of substitution is as follows:##STR12##

Preferred ligands are:

1-indenyl, 2-alkyl-4-aryl-1-indenyl, 2,4-dialkyl-1-indenyl,2,4-diaryl-1-indenyl, 2,4,6-trialkyl-1-indenyl,1-alkyl-α-acenaphth-1-indenyl, 1-alkyl-4,5-benzo-1-indenyl,2,5-dialkyl-1-indenyl, 2,5,6-trialkyl-1-indenyl,2,4,5-trialkyl-1-indenyl, 2-alkyl-1-indenyl, 2-aryl-1-indenyl,2,6-dialkyl-4-aryl-1-indenyl,2-alkyl-5-aryl-2-alkyl-5,6-diaryl-1-indenyl,2-alkyl-4,5-diaryl-1-indenyl, 2-alkyl-4,6-diaryl-1-indenyl, fluorenyl,2,7-dialkylfluorenyl, or 4-alkylfluorenyl, 2-alkyl-1-cyclopentadienyl,2,4-dialkyl-1-cyclopentadienyl, 2,4,5-trialkyl-1-cyclopentadienyl,2-Si(trialkyl)-1-cyclopentadienyl,2-Si(trialkyl)-4-alkyl-1-cyclopentadienyl,2-Si(trialkyl)-4,5-dialkyl-1-cyclopentadienyl,2-alkyl-4-aryl-1-cyclopentadienyl, 2,5-alkyl-4-aryl-1-cyclopentadienyl,2,4-alkyl-5-aryl-1-cyclopentadienyl, 2-aryl-1-cyclopentadienyl,2-aryl-4-alkyl-1-cyclopentadienyl, 2-aryl-4,5-alkyl-1-cyclopenta-dienylor 2-alkyl-4,5-aryl-1-cyclopentadienyl.

The following examples are intended to illustrate in more detail thecompounds described by the formula I. However, the list is not claimedto be complete:

1,6-bis[methylsilyl(fluorenyl)(cyclopentadienyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl(indenyl)(cyclopentadienyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl(fluorenyl)(3-methylcyclopentadienyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl(indenyl)(3-methylcyclopentadienyl)zirconiumdichloride ]hexane,

1,6-bis[methylsilyl-(fluorenyl)(3-isopropylcyclopentadienyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(indenyl)(3-isopropylcyclopentadienyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(2-methylindenyl)(cyclopentadienyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(cyclopentadienyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(4-phenylindenyl)(cyclopentadienyl)-zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(fluorenyl)(3-phenylcyclopentadienyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(indenyl)(3-phenylcyclopentadienyl)-zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(2-methyl-4,5-benzoindenyl)(cyclopentadienyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(2-methyl-4,6-diisopropylindenyl)(cyclopentadienyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(2-methyl-4-(1-naphthylindenyl)-(cyclopentadienyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(2-ethyl-4-phenylindenyl)(cyclopentadienyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(2-methyl-4,5-benzoindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(2-methyl-4,6-diisopropylindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(2-methyl-4-(1-naphthylindenyl)-(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(2-ethyl-4-phenylindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride]hexane,

1,2-bis[methylsilyl-(fluorenyl)(cyclopentadienyl)-zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(indenyl)(cyclopentadienyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(fluorenyl)(3-methylcyclopenta-dienyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(indenyl)(3-methylcyclopentadienyl)-zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(fluorenyl)(3-isopropylcyclopentadienyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(indenyl)(3-isopropylcyclopentadienyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(2-methylindenyl)(cyclopentadienyl)-zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(cyclopentadienyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(4-phenylindenyl)(cyclopentadienyl)-zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(fluorenyl)(3-phenylcyclopentadienyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(indenyl)(3-phenylcyclopentadienyl)-zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(2-methyl-4,5-benzoindenyl)(cyclopentadienyl)zirconiumdichloride]ethane,

1,2-bis[methylsily-(2-methyl-4,6-diisopropylindenyl)-(cyclopentadienyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(2-methyl-4-(1-naphthylindenyl)-(cyclopentadienyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(2-ethyl-4-phenylindenyl)(cyclopentadienyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(2-methyl-4,5-benzoindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(2-methyl-4,6-diisopropylindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride]-ethane,

1,2-bis[methylsilyl-(2-methyl-4-(1-naphthylindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride]-ethane,

1,2-bis[methylsilyl-(2-ethyl-4-phenylindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride]ethane,

1,4-disilacyclohexane-1,4-diylidene[(fluorenyl)(cyclopentadienyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(indenyl)(cyclopentadienyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(fluorenyl)(3-methylcyclopentadienyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(indenyl)(3-methylcyclopentadienyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(fluorenyl)(3-isopropylcyclopentadienyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(indenyl)(3-isopropylcyclopentadienyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(2-methylindenyl)(cyclopentadienyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenylindenyl)(cyclopentadienyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(4-phenylindenyl)(cyclopentadienyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenyl-indenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(fluorenyl)(3-phenylcyclopentadienyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(indenyl)(3-phenylcyclopentadienyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4,5-benzoindenyl)(cyclopentadienyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4,6-diisopropylindenyl)(cyclopentadienyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-(1-napthylindenyl)(cyclopentadienyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(2-ethyl-4-phenylindenyl)(cyclopentadienyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4,5-benzo-indenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4,6-diiso-propylindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-(1-naphthylindenyl)(2,3,5-trimethylcyclopentadienyl)-zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(2-ethyl-4-phenyl-indenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(fluorenyl)(cyclopentadienyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(indenyl)(cyclopentadienyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene-[(fluorenyl)(3-methylcyclopentadienyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(indenyl)(3-methylcyclopentadienyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene-[(fluorenyl)(3-isopropylcyclopentadienyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene-[(indenyl)(3-isopropylcyclopentadienyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methylindenyl)(cyclopentadienyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-phenylindenyl)(cyclopentadienyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(4-phenylindenyl)(cyclopentadienyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-phenylindenyl)(2,3,5-trimethylcyclopentadienyl)-zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(fluorenyl)(3-phenylcyclopentadienyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(indenyl)(3-phenylcyclopentadienyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4,5-benzoindenyl)(cyclopentadienyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4,6-diisopropylindenyl)(cyclopentadienyl)-zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-(1-naphthylindenyl)(cyclopentadienyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-ethyl-4-phenylindenyl)(cyclopentadienyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4,5-benzoindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4,6-diisopropylindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-(1-naphthylindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-ethyl-4-phenylindenyl)(2,3,5-trimethylcyclopentadienyl)-zirconiumdichloride],

1,6-bis[methylsilyl-bis(indenyl)zirconium dichloride]hexane,

1,6-bis[methylsilyl-bis(2-methylindenyl)zirconium dichloride]hexane,

1,6-bis[methylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-bis(2-methyl-4,5-benzoindenyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-bis(2-methyl-4-(1-naphthyl)indenyl)-zirconiumdichloride]hexane,

1,6-bis[methylsilyl-bis(2-methyl-4-isopropylindenyl)-zirconiumdichloride]hexane,

1,6-bis[methylsilyl-bis(2-methyl-4,6-diisopropylindenyl)-zirconiumdichloride]hexane,

1,6-bis[methylsilyl-bis(2-ethylindenyl)zirconium dichloride]hexane,

1,6-bis[methylsilyl-bis(2-ethyl-4-phenylindenyl)-zirconiumdichloride]hexane,

1,6-bis[methylsilyl-bis(2-ethyl-4-(1-naphthyl)indenyl)-zirconiumdichloride]hexane,

1,6-bis[methylsilyl-bis(2-ethyl-α-acenaphthindenyl)-zirconiumdichloride]hexane,

1,2-bis[methylsilyl-bis(indenyl)zirconium dichloride]ethane,

1,2-bis[methylsilyl-bis(2-methylindenyl)zirconium dichloride]ethane,

1,2-bis[methylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-bis(2-methyl-4,5-benzoindenyl)-zirconiumdichloride]ethane,

1,2-bis[methylsilyl-bis(2-methyl-4-(1-naphthyl)indenyl)-zirconiumdichloride]ethane,

1,2-bis[methylsilyl-bis(2-methyl-4-isopropylindenyl)-zirconiumdichloride]ethane,

1,2-bis[methylsilyl-bis(2-methyl-4,6-diisopropylindenyl)-zirconiumdichloride]ethane,

1,2-bis[methylsilyl-bis(2-ethylindenyl)zirconium dichloride]ethane,

1,2-bis[methylsilyl-bis(2-ethyl-4-phenylindenyl)-zirconiumdichloride]ethane,

1,2-bis[methylsilyl-bis(2-ethyl-4-(1-naphthyl)indenyl)-zirconiumdichloride]ethane,

1,2-bis[methylsilyl-bis(2-ethyl-α-acenaphthindenyl)-zirconiumdichloride]ethane,

1,2-bis[ethylsilyl-bis(indenyl)zirconium dichloride]ethane,

1,2-bis[ethylsilyl-bis(2-methylindenyl)zirconium dichloride]ethane,

1,2-bis[ethylsilyl-bis(2-methyl-4-phenylindenyl)-zirconiumdichloride]ethane,

1,2-bis[ethylsilyl-bis(2-methyl-4,5-benzoindenyl)-zirconiumdichloride]ethane,

1,2-bis[ethylsilyl-bis(2-methyl-4-(1-naphthyl)indenyl)-zirconiumdichloride]ethane,

1,2-bis[ethylsilyl-bis(2-methyl-4-isopropylindenyl)-zirconiumdichloride]ethane,

1,2-bis[ethylsilyl-bis(2-methyl-4,6-diisopropylindenyl)-zirconiumdichloride]ethane,

1,2-bis[ethylsilyl-bis(2-ethylindenyl)zirconium dichloride]ethane,

1,2-bis[ethylsilyl-bis(2-ethyl-4-phenylindenyl)zirconiumdichloride]ethane,

1,2-bis[ethylsilyl-bis(2-ethyl-4-(1-naphthyl)indenyl)-zirconiumdichloride]ethane,

1,2-bis[ethylsilyl-bis(2-ethyl-α-acenaphthindenyl)-zirconiumdichloride]ethane,

1,6-bis[ethylsilyl-bis(indenyl)zirconium dichloride]hexane,

1,6-bis[ethylsilyl-bis(2-methylindenyl)zirconium dichloride]hexane,

1,6-bis[ethylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdichloride]hexane,

1,6-bis[ethylsilyl-bis(2-methyl-4,5-benzoindenyl)zirconiumdichloride]hexane,

1,6-bis[ethylsilyl-bis(2-methyl-4-(1-naphthyl)indenyl)-zirconiumdichloride]hexane,

1,6-bis[ethylsilyl-bis(2-methyl-4-isopropylindenyl)zirconiumdichloride]hexane,

1,6-bis[ethylsilyl-bis(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride]hexane,

1,6-bis[ethylsilyl-bis(2-ethylindenyl)zirconium dichloride]hexane,

1,6-bis[ethylsilyl-bis(2-ethyl-4-phenylindenyl)zirconiumdichloride]hexane,

1,6-bis[ethylsilyl-bis(2-ethyl-4-(1-naphthyl)indenyl)zirconiumdichloride]hexane,

1,6-bis[ethylsilyl-bis(2-ethyl-α-acenaphthindenyl)zirconiumdichloride]hexane,

1,3-bis[methylsilyl-bis(indenyl)zirconium dichloride]-propane,

1,3-bis[methylsilyl-bis(2-methylindenyl)zirconium dichloride]propane,

1,3-bis[methylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdichloride]propane,

1,3-bis[methylsilyl-bis(2-methyl-4,5-benzoindenyl)zirconiumdichloride]propane,

1,3-bis[methylsilyl-bis(2-methyl-4-(1-naphthyl)indenyl)-zirconiumdichloride]propane,

1,3-bis[methylsilyl-bis(2-methyl-4-isopropylindenyl)zirconiumdichloride]propane,

1,3-bis[methylsilyl-bis(2-methyl-4,6-diisopropylindenyl)-zirconiumdichloride]propane,

1,3-bis[methylsilyl-bis(2-ethylindenyl)zirconium dichloride]propane,

1,3-bis[methylsilyl-bis(2-ethyl-4-phenylindenyl)zirconiumdichloride]propane,

1,3-bis[methylsilyl-bis(2-ethyl-4-(1-naphthyl)indenyl)zirconiumdichloride]propane,

1,3-bis[methylsilyl-bis(2-ethyl-α-acenaphthindenyl)zirconiumdichloride]propane,

1,4-disilacyclohexane-1,4-diylidene[bis(indenyl)zirconium dichloride],

1,4-disilacyclohexane-1,4-diylidene[bis(2-methylindenyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[bis(2-ethylindenyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[bis(2-methyl-4-phenylindenyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[bis(2-methyl-4-(1-naphthylindenyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[bis(2-methyl-4-isopropylindenyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[bis(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[bis(2-methyl-4,5-benzoindenyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[bis(2-ethyl-4-phenyl-indenyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[bis(2-methyl-α-acenaphthindenyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[bis(indenyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[bis(2-methylindenyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[bis(2-ethylindenyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[bis(2-methyl-4-phenylindenyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[bis(2-methyl-4-(1-naphthylindenyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[bis(2-methyl-4-isopropylindenyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[bis(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[bis(2-methyl-4,5-benzoindenyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[bis(2-ethyl-4-phenylindenyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[bis(2-methyl-α-acenaphthindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disilabenzene-1,4-diylidene[bis(indenyl)zirconiumdichloride],

1,4-dihydro-1,4-disilabenzene-1,4-diylidene[bis(2-methyl-indenyl)zirconiumdichloride],

1,4-dihydro-1,4-disilabenzene-1,4-diylidene[bis(2-ethyl-indenyl)zirconiumdichloride],

1,4-dihydro-1,4-disilabenzene-1,4-diylidene[bis(2-methyl-4-phenylindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disilabenzene-1,4-diylidene[bis(2-methyl-4-(1-naphthylindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disilabenzene-1,4-diylidene[bis(2-methyl-4-isopropylindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disilabenzene-1,4-diylidene[bis(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disilabenzene-1,4-diylidene[bis(2-methyl-4,5-benzoindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disilabenzene-1,4-diylidene[bis(2-ethyl-4-phenylindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disilabenzene-1,4-diylidene[bis(2-methyl-α-acenaphthindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disila-2,3,5,6-tetraphenylbenzene-1,4-diylidene[bis(indenyl)zirconiumdichloride],

1,4-dihydro-1,4-disila-2,3,5,6-tetraphenylbenzene-1,4-diylidene[bis(2-methylindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disila-2,3,5,6-tetraphenylbenzene-1,4-diylidene[bis(2-ethylindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disila-2,3,5,6-tetraphenylbenzene-1,4-diylidene[bis(2-methyl-4-phenylindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disila-2,3,5,6-tetraphenylbenzene-1,4-diylidene[bis(2-methyl-4-(1-naphthylindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disila-2,3,5,6-tetraphenylbenzene-1,4-diylidene[bis(2-methyl-4-isopropylindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disila-2,3,5,6-tetraphenylbenzene-1,4-diylidene[bis(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disila-2,3,5,6-tetraphenylbenzene-1,4-diylidene[bis(2-methyl-4,5-benzoindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disila-2,3,5,6-tetraphenylbenzene-1,4-diylidene[bis(2-ethyl-4-phenylindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disila-2,3,5,6-tetraphenylbenzene-1,4-diylidene[bis(2-methyl-α-acenaphthindenyl)zirconiumdichloride],

1,6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methylindenyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(indenyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-4,5-benzoindenyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-4-(1-naphthyl)indenyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-4-isopropylindenyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-ethyl-indenyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-ethyl-4-phenylindenyl)zirconiumdichloride]hexane,

1,6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-α-acenaphthindenyl)zirconiumdichloride]hexane,

1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(indenyl)-zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-indenyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-4,5-benzoindenyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-4,5-benzoindenyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-4-(1-naphthyl)indenyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-4-isopropylindenyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-ethyl-indenyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-ethyl-4-phenylindenyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-ethyl-4-(1-naphthyl)indenyl)zirconiumdichloride]ethane,

1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-α-acenaphthindenyl)zirconiumdichloride]ethane,

1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenylindenyl)(indenyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methylindenyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-ethylindenyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4-(1-naphthylindenyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4-isopropylindenyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4,5-benzoindenyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenylindenyl(2-ethyl-4-phenylindenyl)zirconiumdichloride],

1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-.alpha.-methylacenaphthindenyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-phenylindenyl)(indenyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-phenylindenyl)(2-methylindenyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-phenylindenyl)(2-ethylindenyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4-isopropylindenyl)zirconiumdichloride

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4,5-benzoindenyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-phenylindenyl)(2-ethyl-4-phenylindenyl)zirconiumdichloride],

9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-α-acenaphthindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disilabenzene-1,4-diylidene[(2-methyl-4-phenylindenyl)(indenyl)zirconiumdichloride],

1,4-dihydro-1,4-disilabenzene-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methylindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disilabenzene-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-ethylindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disilabenzene-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4-(1-naphthylindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disilabenzene-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4-isopropylindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disilabenzene-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disilabenzene-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4,5-benzoindenyl)zirconiumdichloride],

1,4-dihydro-1,4-disilabenzene-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-ethyl-4-phenylindenyl)zirconiumdichloride]and

1,4-dihydro-1,4-disilabenzene-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-α-acenaphthindenyl)zirconiumdichloride].

The preparation of the metallocenes of the invention is illustrated bythe following reaction scheme. ##STR13##

If desired, radicals X which are not halogen can be introduced into themetallocene A4, for example by reaction with alkylating agents such asmethyllithium, to obtain metallocenes of the formula I in which X is nothalogen.

The indene derivatives are commercially available or can be prepared bymethods known in the literature (EP 567 952, EP 545 304).

The processes for preparing the ligand systems and the reaction to givethe bridged metallocenes of the formula I is known in principle (EP 574597, EP 320 762, EP 376 154).

For this purpose, LH and L'H are deprotonated with a strong base, suchas, for example, butyllithium or potassium hydride, in an inert solventand reacted with a reagent of the formula A2 to give the ligand systemof the formula A3 or one of its isomers, with the double bond in thefive-membered ring being able to lie either between C(2) and C(3) orbetween C(1) and C(2). The ligand system is subsequently deprotonatedwith 2 k equivalents of a strong base such as, for example, butyllithiumor potassium hydride in an inert solvent and reacted with k equivalentsof a metal tetrahalide such as, for example, zirconium tetrachloride ina suitable solvent to give A4. Suitable solvents are aliphatic oraromatic solvents such as, for example, hexane or toluene, ethericsolvents such as, for example, tetrahydrofuran or diethyl ether orhalogenated hydrocarbons such as, for example, methylene chloride orhalogenated aromatic hydrocarbons such as, for example,o-dichlorobenzene. It is also possible to use a mixture of a pluralityof metal halides, for example zirconium tetrachloride and hafniumtetrachloride. In this way, polynuclear metallocenes which bear variousmetals in one molecule are obtained.

The present invention also provides a process for preparing an olefinpolymer by polymerization of at least one olefin in the presence of acatalyst containing at least one polynuclear metallocene and at leastone cocatalyst, wherein the polynuclear metallocene is a compound of theformula I.

The polymerization can be a homopolymerization or a copolymerization.Preferably, olefins of the formula R^(a) --CH═CH--R^(b) arehomopolymerized or copolymerized, where R^(a) and R^(b) are identical ordifferent and are a hydrogen atom or a hydrocarbon radical having from 1to 20 carbon atoms, in particular from 1 to 10 carbon atoms, or R^(a)and R^(b) together with the atoms connecting them form one or morerings. Examples of such olefins are 1-olefins such as ethylene,propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or1-octene, styrene, dienes such as 1,3-butadiene or 1,4-hexadiene andcyclic olefins such as norbornene, tetracyclododecene, norbornadiene orvinylnorbornene.

In the process of the invention, preference is given to homopolymerizingethylene or propylene, or copolymerizing ethylene with one or more1-olefins having 3-20 carbon atoms, such as propylene, and/or one ormore dienes having 4-20 carbon atoms, such as 1,3-butadiene. Examples ofcopolymers are ethylene/propylene copolymers andethylene/propylene/1,4-hexadiene copolymers,ethylene/propylene/5-ethylidene-2-norbornene-copolymers andethylene-norbornene-copolymers.

The catalyst used in the process of the invention preferably comprises apolynuclear metallocene of the formula I and a cocatalyst. It is alsopossible to use mixtures of the polynuclear metallocenes of theinvention with mononuclear metallocenes. In principle, the cocatalyst inthe process of the invention can be any compound which, owing to itsLewis acidity, can convert the neutral metallocene into a cation andstabilize it ("lablie coordination"). Furthermore, the cocatalyst or theanion formed therefrom should undergo no further reactions with themetallocene cation formed (EP 427 697). The cocatalyst used ispreferably an aluminum compound and/or a boron compound.

The boron compound preferably has the formula R¹⁶ _(x) NH_(4-x) BR¹⁷ ₄,R¹⁶ _(x) Ph_(4-x) BR¹⁷ ₄, R¹⁶ ₃ CBR¹⁷ ₄ or BR¹⁷ ₃, where x is a numberfrom 1 to 4, preferably 3, the radicals R¹⁶ are identical or different,preferably identical, and are C₁ -C₁₀ -alkyl or C₆ -C₁₈ -aryl, or tworadicals R¹⁶ together with the atoms connecting them form a ring, andthe radicals R¹⁷ are identical or different, preferably identical, andare C₆ -C₁₈ -aryl which can be substituted by alkyl, haloalkyl orfluorine. In particular, R¹⁶ is ethyl, propyl, butyl or phenyl and R¹⁷is phenyl, pentafluorophenyl, 3,5-bistrifluoromethylphenyl, mesityl,xylyl or tolyl (EP 277 003, EP 277 004 and EP 426 638).

The cocatalyst used is preferably an aluminum compound such asaluminoxane and/or an aluminum alkyl.

The cocatalyst used is particularly preferably an aluminoxane, inparticular an aluminoxane of the formula IIIa for the linear type and/orthe formula IIIb for the cyclic type, ##STR14## where in the formulaeIIIa and IIIb, the radicals R¹⁸ can be identical or different and are aC₁ -C₆ -alkyl group, a C₆ -C₁₈ -aryl group, benzyl or hydrogen, and p isan integer from 2 to 50, preferably from 10 to 35.

The radicals R¹⁸ are preferably identical and are methyl, isobutyl,phenyl or benzyl, particularly preferably methyl.

If the radicals R¹⁸ are different, they are preferably methyl andhydrogen or alternatively methyl and isobutyl, with hydrogen or isobutylpreferably being present in an amount of from 0.01 to 40% (number of theradicals R¹⁸).

The processes for preparing the aluminoxanes are known.

Regardless of the method of preparation, all aluminoxane solutions havein common a varying content of unreacted aluminum starting compound,which is present in free form or as an adduct.

It is possible to preactivate the metallocene prior to use in thepolymerization reaction using an aluminoxane of the formula IIIa and/orIIIb. This significantly increases the polymerization activity andimproves the grain morphology. The preactivation of the transition metalcompound is carried out in solution. Preferably, the metallocene is heredissolved in a solution of the aluminoxane in an inert hydrocarbon.Suitable inert hydrocarbons are aliphatic or aromatic hydrocarbons.Preference is given to using toluene.

The concentration of the aluminoxane in the solution is in the rangefrom about 1% by weight to the saturation limit, preferably from 5 to30% by weight, in each case based on the total amount of solution. Themetallocene can be used in the same concentration, but it is preferablyused in an amount of 10⁻⁴ -1 mol per mole of aluminoxane. Thepreactivation takes from 5 minutes to 60 hours, preferably from 5 to 60minutes. It is carried out at a temperature of from -78° to 100° C.,preferably from 0° to 70° C.

A prepolymerization can be carried out with the aid of the metallocene.For the prepolymerization, preference is given to using the (or one ofthe) olefin(s) used in the polymerization.

To control the grain morphology, the metallocene can also be applied toa support. Suitable support materials are, for example, silica gels,aluminum oxides, solid aluminoxane or other inorganic support materialssuch as, for example, magnesium chloride. Polyolefin powder in finelydivided form is also a suitable support material. The preparation of thesupported catalyst can be carried out, for example, as described in EP578 838.

When using the abovementioned cocatalysts, the actual (active)polymerization catalyst is the reaction product of metallocene and oneof the specified compounds. For this reason, this reaction product ispreferably first prepared outside the polymerization reactor in aseparate step using a suitable solvent.

To remove catalyst poisons present in the olefin, purification using analuminum alkyl, for example trimethyl-aluminum or triethylaluminum isadvantageous. This purification can either be carried out in thepolymerization system itself, or the olefin is, prior to addition to thepolymerization system, brought into contact with the aluminum compoundand is subsequently separated off again.

The polymerization is carried out in a known manner in solution, insuspension or in the gas phase, continuously or batchwise, in one ormore stages at a temperature of from -60° to 250° C., preferably from30° to 100° C., particularly preferably from 50° to 80° C.

As molecular weight regulator and/or to increase the activity, hydrogenis added if necessary. The total pressure in the polymerization systemis from 0.5 to 100 bar. Preference is given to polymerization in thepressure range from 5 to 64 bar, which is particularly important inindustry.

In this polymerization, the metallocene is used in a concentration,based on the transition metal, of from 10⁻³ to 10⁻⁸ mol, preferably from10⁻⁴ to 10⁻⁷ mol, of transition metal per dm³ of solvent or per dm³ ofreactor volume. The aluminoxane is used in a concentration of from 10⁻⁵to 10⁻¹ mol, preferably from 10⁻⁴ to 10⁻² mol, per dm³ of solvent or perdm³ of reactor volume. The other specified cocatalysts are used inapproximately equimolar amounts to the metallocene. In principlehowever, higher concentrations are also possible.

If the polymerization is carried out as suspension or solutionpolymerization, an inert solvent customary for the Ziegler low-pressureprocess is used. For example, it is carried out in an aliphatic orcycloaliphatic hydrocarbon; examples of such which may be mentioned arepropane, butane, hexane, heptane, isooctane, cyclohexane,methylcyclohexane. Furthermore, a gasoline or hydrogenated diesel oilfraction can be employed. It is also possible to use toluene.Preferably, polymerization is carried out in the liquid monomer.

If inert solvents are used, the monomers are metered in in gaseous orliquid form.

The duration of polymerization can be any desired, since the catalystsystem to be used according to the invention shows only a lowtime-dependent fall in the polymerization activity.

The polymers prepared by the process of the invention are suitable forthe production of semi-finished parts and extruded shaped parts such asfilms, sheets or large hollow bodies (e.g. pipes). With appropriateselection of the monomers, it is also possible to prepare rubbers orelastomers.

In the process of the invention, the metallocenes described produce, inthe temperature range from 50° to 80° C. which is of particularimportance in industry and at high catalyst activities, polymers havinga very high molecular weight, in the case of prochiral monomers veryhigh molecular weight and very high stereotacticity. In addition, acomplicated isomer separation can be omitted for the metallocenesynthesis.

In particular, in the case of the stereospecific polymerization ofprochiral olefins, for example of propylene, the metallocene of theinvention gives polymers having high stereoregularity and molecularweight. Particularly in the case of the isospecific polymerization ofpropylene, it gives isotactic polypropylene having high isotacticsequence lengths and a high melting point.

If the metallocene of the invention has different types of centralatoms, polyolefins having a broad, bimodal or polymodal molecular weightdistribution are obtained.

Furthermore, reactor deposits can be avoided using the metallocene ofthe invention, without the catalyst having to be supported.

In addition, the metallocene of the invention is suitable for preparingethylene-containing copolymers such as rubbers or elastomers having ahigh proportion of comonomer and particularly regular incorporation ofcomonomer.

The following examples illustrate the invention in more detail.

All glass apparatus was baked out in vacuo and flushed with argon. Alloperations were carried out with exclusion of moisture and oxygen inSchlenk vessels. The solvents used were in each case freshly distilledunder argon over Na/K alloy and stored in Schlenk vessels.

The Al/CH₃ ratio in the aluminoxane was determined by decomposition ofthe sample with H₂ SO₄ and determination of the volume of the hydrolysisgases formed under standard conditions and also by complexometrictitration of the aluminum in the then dissolved sample by theSchwarzenbach method.

Toluene-soluble methylaluminoxane was used as a 10% strength by weighttoluene solution for the examples of suspension polymerization and ofbulk polymerization using unsupported metallocene and contained 36 mgAl/cm³, according to the aluminum determination. The mean degree ofoligomerization according to freezing point depression in benzene wasn=20. For the toluene-soluble methyl-aluminoxane, an Al:CH₃ ratio of1:1.55 was found.

Definitions:

VN=viscosity number in cm³ /g

M_(w) =weight average molecular weight in g/mol (determined by gelpermeation chromatography)

M_(w) /M_(n) =polydispersity

Mp.=melting point in °C. (determined by DSC, 20° C./min heating/coolingrate )

II=isotactic index (II=mm+1/2 mr, determined by ¹³ C-NMR spectroscopy)

MFI 230/5=melt flow index, measured in accordance with DIN 53735; indg/min

BD=polymer bulk density in g/dm³.

Synthesis of the metallocenes used in the polymerization examples (thestarting materials used are commercially available):

A. 1,6-bis[methylsilyl-bis(2-methyl-4-phenylindenyl)-zirconiumdichloride]hexane (1)

36.1 ml (97 mmol) of a 20% strength solution of butyl-lithium in toluenewere added dropwise at room temperature over a period of 30 minutes to asolution of 20 g (97 mmol) of 2-methyl-7-phenylindene in 200 ml of O₂-free and H₂ O-free toleuene and 10 ml of oxygen-free anhydrous THFunder an argon atmosphere. After addition was complete, the mixture washeated for a further 2 hours at 80° C. Subsequently, 7.6 g (24.3 mmol)of 1,6-bis(methyldichlorosilyl)hexane in 10 ml of toluene were addeddropwise at from 0° to 5° C. over a period of 30 minutes and the mixturewas stirred for a further 1.5 hours at room temperature. For the workup,100 ml of water were added, the phases were separated and the organicphase was freed of solvent. After filtration through 200 g of silica gel(hexane/CH₂ Cl₂ 5:1), 11.7 g (48%) of the ligand system were obtained asa viscous oil.

22 ml (59 mmol) of a 20% strength solution of butyllithium in toluenewere added dropwise at room temperature under an argon atmosphere over aperiod of 30 minutes to a solution of 11.7 g (12 mmol) of ligand in 150ml of oxygen-free anhydrous diethyl ether. After addition was complete,the mixture was heated under reflux for a further 2 hours, the solventwas removed in vacuo and the residue was filtered using hexane through aG3 Schlenk frit. The tetralithium salt was dried for a number of hoursin an oil pump vacuum at room temperature and subsequently added at -78°C. to a suspension of 5.5 g (24 mmol) of zirconium tetrachloride in 200ml of oxygen-free anhydrous CH₂ Cl₂. The cooling bath was removed andthe mixture was stirred for a further 1 hour at room temperature. Thereaction mixture was filtered through a G3 Schlenk frit, the filtratewas freed of solvent in vacuo and the residue was washed a number oftimes with hexane. Subsequently, it was recrystallized from toluene at-30° C. This gave 7.3 g (47%) of 1 as isomer mixture in the form of ayellow amorphous solid.

¹ H-NMR (100 MHz), CDCl₃): 6.8 to 7.8 (m, 36H, arom. H and β-H-indene);2.1 and 2.3 (2 m, 12H, CH₃ -indene); 1.2 to 2.0 (m, 18H, 4CH₂, CH₂ Siand CH₃ Si). Mass spectrum: 1306M⁺, correct disintegration pattern.

B. 1,2-bis[methylsilyl-bis(2-methyl-4-phenylindenyl)-zirconiumdichloride]ethane (2)

36.1 ml (97 mmol) of a 20% strength solution of butyl-lithium in toluenewere added dropwise at room temperature over a period of 30 minutes to asolution of 20 g (97 mmol) of 2-methyl-7-phenylindene in 200 ml ofoxygen-free anhydrous toluene and 10 ml of O₂ -free and H₂ O-freeanhydrous THF under an argon atmosphere. After addition was complete,the mixture was heated for a further 2 hours at 80° C. Subsequently, 6.2g (24.2 mmol) of 1,2-bis(methyldichlorosilyl)ethane in 10 ml of toluenewere added dropwise at from 0° to 5° C. over a period of 30 minutes andthe mixture was stirred for a further 1.5 hours at room temperature. Forthe workup, 100 ml of water were added, the phases were separated andthe organic phase was freed of solvent. After filtration through 200 gof silica gel (hexane/CH₂ Cl₂ 5:1), 11.8 g (52%) of the ligand systemwere obtained as a viscous oil.

21.5 ml (57.6 mmol) of a 20% strength solution of butyllithium intoluene were added dropwise at room temperature under an argonatmosphere over a period of 30 minutes to a solution of 10.8 g (11 mmol)of ligand in 150 ml of oxygen-free anhydrous diethyl ether. Afteraddition was complete, the mixture was heated under reflux for a further2 hours, the solvent was removed in vacuo and the residue was filteredusing hexane through a G3 Schlenk frit. The tetralithium salt was driedfor a number of hours in an oil pump vacuum at room temperature andsubsequently added at -78° C. to a suspension of 5.4 g (23 mmol) ofzirconium tetrachloride in 200 ml of oxygen-free anhydrous CH₂ Cl₂. Thecooling bath was removed and the mixture was stirred for a further 1hour at room temperature. The reaction mixture was filtered through a G3Schlenk frit, the filtrate was freed of solvent in vacuo and the residuewas washed a number of times with hexane. Subsequently, it wasrecrystallized from toluene at -30° C. This gave 5.6 g (39%) of 2 asisomer mixture in the form of a yellow amorphous solid.

¹ H-NMR (100 MHz), CDCl₃): 6.9 to 7.8 (m, 36H, arom. H and β-H-indene);2.3 and 2.5 (2 m, 12H, CH₃ -indene); 1.2 to 1.7 (m, 10H, CH₂ Si and CH₃Si). Mass spectrum: 1250M⁺, correct disintegration pattern.

C.1,6-bis[methylsilyl-(2-methylindenyl)(2-methyl-4-phenylindenyl)zirconiumdichloride]hexane (3)

27 ml (73 mmol) of a 20% strength solution of butyl-lithium in toluenewere added dropwise at room temperature over a period of 30 minutes to asolution of 15 g (73 mmol) of 2-methyl-7-phenylindene in 150 ml oftoluene and 10 ml of THF. After addition was complete, the mixture washeated for a further 2 hours at 80° C. Subsequently, 11.2 g (36 mmol) of1,6-bis(methyldichlorosilyl)hexane in 10 ml of toluene were addeddropwise at from 0° to 5 ° C. over a period of 2 minutes and the mixturewas stirred for a further 1.5 hours at room temperature. The solventswere removed and the residue was taken up in toluene and precipitatedLiCl was subsequently filtered off. A suspension of2-methylindenyllithium (prepared by reaction of 9.5 g (73 mmol) of2-methylindene in 100 ml of toluene and 20 ml of THF at room temperaturewith 27 ml (73 mmol) of a 20% strength solution of butyllithium intoluene and stirring further for 1 hour at 50° C.) was added dropwise atroom temperature to the filtrate over a period of 30 minutes and themixture was subsequently stirred for a further 2 hours at roomtemperature. The reaction mixture was admixed with 100 ml of water, thephases were separated and the organic phase was washed with 50 ml ofwater. The solvents were removed in vacuo and the residue was purifiedby chromatography on 500 g of silica gel (hexane/methylene chloride1:1). This gave 7.3 g (24%) of the unsymmetric ligand system of compound3 as a very viscous oil.

15 ml (40 mmol) of a 20% strength solution of butyllithium in toluenewere added dropwise at room temperature over a period of 30 minutes to asolution of 7.1 g (8.4 mmol) of the ligand system of compound 3 in 50 mlof diethyl ether. After addition was complete, the mixture was heatedunder reflux for a further 2 hours, the solvent was removed in vacuo andthe residue was filtered using hexane through a G3 Schlenk frit. Thetetralithium salt was dried for a number of hours in an oil pump vacuumat room temperature and subsequently added at -78° C. to a suspension of3.7 g (16 mmol) of zirconium tetrachloride in 50 ml of O₂ -free and H₂O-free CH₂ Cl₂. The cooling bath was removed and the mixture was stirredfor a further 1 hour at room temperature. The reaction mixture wasfiltered through a G3 Schlenk frit, the residue was extracted furtherwith a total of 200 ml of methylene chloride and the combined filtrateswere largely freed of solvent in vacuo. The residue was washed a numberof times with hexane/methylene chloride 1:1 and subsequently dried. Thisgave 4.2 g (43%) of compound 3 as a yellow amorphous solid.

¹ H-NMR (100 MHz, CDCl₃): 6.7 to 8.0 (m, 28H, arom. H and β-indH); 2.1and 2.3 (2 m, 12H, CH₃ -indene); 1.2-2.0 (m, 18H, 4CH₂, CH₂ Si and CH₃Si).

D. 1,2-bis[methylsilyl-(indenyl)(2-methyl-4-phenyl-indenyl)zirconiumdichloride]ethane (4)

27 ml (73 mmol) of a 20% strength solution of butyllithium in toluenewere added dropwise at room temperature to a solution of 15 g (73 mmol)of 2-methyl-7-phenylindene in 150 ml of toluene and 8 ml of THF over aperiod of 30 minutes. After addition was complete, the mixture washeated to 80° C. for a further 2 hours. Subsequently, 11.2 g (36 mmol)of 1,2-bis(methyldichlorosilyl)ethane in 10 ml of toluene were addeddropwise at from 0° to 5° C. over a period of 2 minutes and the mixturewas stirred for a further 1.5 hours at room temperature. The solventswere removed and the residue was taken up in toluene and precipitatedLiCl was subsequently filtered off. A suspension of indenyllithium(prepared by reacting 8.5 g (73 mmol) of indene in 100 ml of toluene and20 ml of THF at room temperature with 27 ml (73 mmol) of a 20% strengthsolution of butyllithium in toluene and stirring further for 1 hour at50° C.) was added dropwise at room temperature to the filtrate over aperiod of 30 minutes and the mixture was subsequently stirred for afurther 2 hours at room temperature. The reaction mixture was admixedwith 100 ml of water, the phases were separated and the organic phasewas washed with 50 ml of water. The solvents were removed in vacuo andthe residue was purified by chromatography on 500 g of silica gel(hexane/methylene chloride 1:1). This gave 9.3 g (31%) of theunsymmetric ligand system of compound 4 as a very viscous oil.

17 ml (46 mmol) of a 20% strength solution of butyllithium in toluenewere added dropwise at room temperature to a solution of 9.1 g (11 mmol)of the ligand system of compound 4 in 150 ml of diethyl ether over aperiod of 30 minutes. After addition was complete, the mixture washeated under reflux for a further 2 hours, the solvent was removed invacuo and the residue was filtered using hexane through a G3 Schlenkfrit. The tetralithium salt was dried for a number of hours in an oilpump vacuum at room temperature and subsequently added at -78° C. to asuspension of 4.9 g (21 mmol) of zirconium tetrachloride in 200 ml ofCH₂ Cl₂. The cooling bath was removed and the mixture was stirred for afurther 1 hour at room temperature. The reaction mixture was filteredthrough a G3 Schlenk frit, the residue was extracted further with atotal of 400 ml of methylene chloride and the combined filtrates werelargely freed of solvent in vacuo. The residue was washed a number oftimes with 10 ml of methylene chloride each time and was subsequentlydried. This gave 4.3 g (34%) of compound 4 as a yellow amorphous solid.

¹ H-NMR (100 MHz, CDCl₃): 6.9-7.8 (m, 28H, arom. H and β-indH); 6.3 (m,2H, α-indH), 2.4 (m, 6H, CH₃ -indene); 1.2-2.0 (m, 18H, 4CH₂, CH₂ Si andCH₃ Si).

E.1,6-bis[methylsilyl-(2,3,5-trimethylcyclopenta-dienyl)(2-methyl-4-phenylindenyl)zirconiumdichloride]hexane (5)

27 ml (73 mmol) of a 20% strength solution of butyllithium in toluenewere added dropwise at room temperature to a solution of 15 g (73 mmol)of 2-methyl-7-phenylindene in 150 ml of toluene and 8 ml of THF over aperiod of 30 minutes. After addition was complete, the mixture washeated for a further 2 hours at 80° C. Subsequently, 11.2 g (36 mmol) of1,6-bis(methyldichlorosilyl)hexane in 10 ml of toluene were addeddropwise at from 0° to 5° C. over a period of 2 minutes and the mixturewas stirred for a further 1.5 hours at room temperature. The solventswere removed and the residue was taken up in toluene and precipitatedLiCl was subsequently filtered off. A suspension of1,2,4-trimethylcyclopentadienyllithium (prepared by reacting 7.9 g (73mmol) of 1,2,4-trimethylcyclopentadiene in 100 ml of toluene and 20 mlof THF at room temperature with 27 ml (73 mmol) of a 20% strengthsolution of butyllithium in toluene and stirring for a further 1 hour atroom temperature) was added dropwise at room temperature to the filtrateover a period of 30 minutes and the mixture was subsequently stirred fora further 2 hours at room temperature. The reaction mixture was admixedwith 100 ml of water, the phases were separated and the organic phasewas washed with 50 ml of water. The solvents were removed in vacuo andthe residue was purified by chromatography on 700 g of silica gel(hexane/AcOEt 5:1). This gave 13.5 g (47%) of the ligand system ofcompound 5 as a very viscous oil.

26 ml (70 mmol) of a 20% strength solution of butyllithium in toluenewere added dropwise at room temperature to a solution of 13 g (16.5mmol) of the ligand system of compound 5 in 150 ml of diethyl ether overa period of 30 minutes. After addition was complete, the mixture washeated for a further 2 hours under reflux, the solvent was removed invacuo and the residue was filtered using hexane through a G3 Schlenkfrit. The tetralithium salt was dried for a number of hours in an oilpump vacuum at room temperature and subsequently added at -78° C. to asuspension of 7.5 g (32 mmol) of zirconium tetrachloride in 150 ml ofCH₂ Cl₂. The cooling bath was removed and the mixture was stirred for afurther 1 hour at room temperature. The reaction mixture was filteredthrough a G3 Schlenk frit, the residue was extracted further with atotal of 100 ml of methylene chloride and the combined filtrates werelargely freed of solvent in vacuo. The residue was washed a number oftimes with hexane and subsequently dried. This gave 6.1 g (36%) ofcompound 5 as a yellow amorphous solid.

¹ H-NMR (100 MHz, CDCl₃): 6.9 to 8.0 (m, 18H, arom. H and β-indH); 6.4(s, 1H, H-Cp), 1.9 to 2.2 (m, 24H, CH₃ -ind and -Cp); 1.2 to 2.0 (m,18H, 4CH₂, CH₂ Si and CH₃ Si).

F.1,6-bis[methylsilyl-(3-isopropylcyclopentadienyl)-(fluorenyl)zirconiumdichloride]hexane (6)

22 ml (60 mmol) of a 22% strength solution of butyllithium in toluenewere added dropwise at room temperature to a solution of 10 g (60 mmol)of fluorene in 100 ml of toluene and 10 ml of diethyl ether over aperiod of 30 minutes. After addition was complete, the mixture washeated for a further 2 hours at 80° C. Subsequently, 7.8 g (30 mmol) of1,6-bis(methyldichlorosilyl)hexane in 10 ml of toluene were addeddropwise at from 0° to 5 ° C. over a period of 2 minutes and the mixturewas stirred for a further 1 hour at room temperature. The solvents wereremoved and the residue was taken up in toluene and precipitated LiClwas subsequently filtered off. A suspension ofisopropylcyclopentadienyllithium (prepared by reacting 6.5 g (60 mmol)of isopropylcyclopentadiene in 100 ml of toluene and 10 ml of diethylether at room temperature with 22 ml (60 mmol) of a 20% strengthsolution of butyllithium in toluene and stirring for a further 1 hour atroom temperature) was added dropwise at room temperature to the filtrateover a period of 30 minutes and the mixture was subsequently stirred fora further 2 hours at room temperature. The reaction mixture was admixedwith 100 ml of water, the phases were separated and the organic phasewas washed with 50 ml of water. The solvents were removed in vacuo andthe residue was purified by chromatography on 700 g of silica gel(hexane/methylene chloride 10:1). This gave 13.3 g (63%) of the ligandsystem of compound 6 as a very viscous oil.

30 ml (80 mmol) of a 20% strength solution of butyllithium in toluenewere added dropwise at room temperature to a solution of 13 g (18 mmol)of the ligand system of compound 6 in 150 ml of diethyl ether over aperiod of 30 minutes. After addition was complete, the mixture washeated for a further 2 hours under reflux, the solvent was removed invacuo and the residue was filtered using hexane through a G3 Schlenkfrit. The tetralithium salt was dried for a number of hours in an oilpump vacuum at room temperature and subsequently added at -78° C. to asuspension of 8.15 g (35 mmol) of zirconium tetrachloride in 150 ml ofmethylene chloride. The cooling bath was removed and the mixture wasstirred for a further 1 hour at room temperature. The reaction mixturewas filtered through a G3 Schlenk frit, the residue was furtherextracted with a total of 300 ml of methylene chloride and the combinedfiltrates were evaporated in vacuo to about 1/3 of their volume. At -20°C., 4.6 g (27%) of compound 6 crystallized therefrom as a yellowamorphous solid.

¹ H-NMR (100 MHz, CDCl₃): 7.1 to 8.2 (m, 16H, arom. H), 5.5, 5.7, 6.3(3m, 6H, H-Cp), 2.9 (m, 2H, i-propyl), 1.0 to 2.0 (m, 30H, 4CH₂, CH₂ Si,CH₃ Si and CH₃ -i-propyl).

G. 1,6-{Bis[methylsilyldiindenyl)zirconiumdichloride]}hexane (7)

20 g (172 mmol)indene, 64.2 ml (172 mmol) butyllithium (20% in toluene)and 12.8 g (42 mmol) 1,6-bis(methyldichlorosilyl)hexane have beenreacted as described in example A. Filtration over 250 g of silica(hexane/methylenechloride 5:1) gave 14.1 g (53%) of the ligand system asa viscous oil.

14.0 g (22 mmol) of the ligand system, 37.3 ml (100 mmol) butyllithium(20% in toluene) and 10.1 g (44 mmol) zirconiumtetrachloride have beenreacted analogous to the procedure described in example A. Complex 3precipitated at -30° C. from a toluene solution as a yellow amorphouspowder. The yield was 9.0 g (43%) 7.

¹ H-NMR (100 MHz, CDCl₃): 6.8 to 7.6 (m, 20H, arom. H und β-H-indene),6.0 to 6.2 (m, 4H, α-H-indene); 1.2 to 2.0 (m, 12H, 4 CH₂ und 2 CH₂ Si);0.9 bis 1.3 (3 s, broad, 6H, Si--CH₃). Mass spectrum: 951M⁺, correctfragmentation pattern.

H.1,6-{Bis[methylsilyl-bis(2-methyl-4,5-benzoindenyl)zirconiumdichloride]}hexane(8)

1,6-{Bis[methylsilyl-bis(2-methyl-4,5-benzoindenyl)zirconiumdichloride]}hexanewas synthesized in the manner as in example A. From the reaction of 57.8g (320 mmol) 2-methyl-4,5-benzoindene, 119 ml (320 mmol) butyllithium(20% by weight in toluene) and 23.5 g (80 mmol)1,6-Bis(methyldichlorosilyl)hexane was obtained 30.2 g (43%) of theligand.

The reaction of 29.6 g (33 mmol) ligand with 50 ml (134 mmol)butyllithium (20% by weight in toluene) and 13.3 g (57 mmol) of ZrCl₄gave 12.4 g (35%) 8.

¹ H-NMR (100 MHz, CDCl₃): 8.0-6.9 (m, 28H, arom. H, b-H-indene); 2.3-2.2(m, 12H, Me-indene); 1,6-1.2 (m, 18H, 6 CH₂ and 2 SiCH₃). Mass spectrum:1207M⁺, correct fragmentation pattern.

I.1,2-{Bis[methylsilyl-bis(2-methyl-4,5-benzoindenyl)zirconiumdichloride]}ethane(9)

1,2-{Bis[methylsilyl-bis(2-methyl-4,5-benzoindenyl)zirconiumdichloride]}ethanewas synthesized in the manner as in example B. From the reaction of 72.7g (403 mmol) 2-methyl-4,5-benzoindene, 150 ml (403 mmol) butyllithium(20% by weight in toluene) and 23.5 g (92 mmol)1,2-bis(methyldichlorosilyl)ethane was obtained 29.8 g (39%) of theligand.

The reaction of 15.7 g (19 mmol) ligand with 30 ml (80 mmol)butyllithium (20% by weight in toluene) and 8.8 g (38 mmol) of ZrCl₄gave 13.5 g (62%) 9.

¹ H-NMR (100 MHz, CDCl₃): 8.0-6.9 (m, 28H, arom. H, b-H-indene); 2.3-2.2(m, 12H, Me-indene); 1.4-1.2 (m, 10H, 2 CH₂ and 2 SiCH₃). Mass spectrum:1151M⁺, correct fragmentation pattern.

Polymerization examples:

EXAMPLE 1

A dry 16 dm³ reactor was first flushed with nitrogen and then withpropylene and charged with 10 dm³ of liquid propylene. 30 cm³ ofmethylaluminoxane solution in toluene were then added and the mixturewas stirred at 30° C. In parallel thereto, 3.4 mg of the metallocene 1were dissolved in 20 cm³ of methylaluminoxane solution in toluene (23mmol Al) and reacted by allowing to stand for 15 minutes. The solutionwas then added to the reactor, heated (4° C./min) to the polymerizationtemperature of 50° C. by supply of heat and the polymerization systemwas maintained at 50° C. for 1 hour by means of cooling. Thepolymerization was stopped by addition of 20 ml of isopropanol, theexcess monomer was vented and the polymer was dried in vacuo. This gave0.17 kg of polypropylene.

The catalyst activity was 50 kg PP/g metallocene·h. VN=1041 cm³ /g;mp.=154° C.; the proportion extractable with heptane was 1.3%; M_(w)/M_(n) =6.4.

EXAMPLE 2

The polymerization of Example 1 was repeated, except that 4.3 mg of themetallocene 1 were used and the polymerization temperature was 60° C.This gave 0.45 kg of polypropylene.

The catalyst activity was 105 kg PP/g metallocene·h. VN=764 cm³ /g;mp.=154° C.; the proportion extractable with heptane is 1.9%; M_(w)/M_(n) =2.9.

EXAMPLE 3

The polymerization of Example 1 was repeated, except that 4.4 mg of themetallocene 1 were used and the polymerization temperature was 70° C.This gave 1.08 kg of polypropylene. The reactor has only very thindeposits on the interior wall and stirrer.

The catalyst activity was 245 kg PP/g metallocene·h. VN=518 cm³ /g;mp.=153° C.; the proportion extractable with heptane is 2.4%; M_(w)/M_(n) =2.7.

EXAMPLE 4

The polymerization of Example 1 was repeated, except that 2.7 mg of themetallocene 2 were used. This gave 0.17 kg of polypropylene.

The catalyst activity was 31 kg PP/g metallocene·h. VN=845 cm³ /g;mp.=154° C.; M_(w) /M_(n) =3.7; the proportion extractable with heptaneis 7.7%.

EXAMPLE 5

The polymerization of Example 1 was repeated, except that 4.3 mg of themetallocene 2 were used and the polymerization temperature was 60° C.This gave 0.71 kg of polypropylene.

The catalyst activity was 74 kg PP/g metallocene·h. VN=564 cm³ /g;mp.=153° C.; M_(w) /M_(n) =3.0; the proportion extractable with heptaneis 4.6%.

EXAMPLE 6

The polymerization of Example 1 was repeated, except that 3.8 mg of themetallocene 2 were used and the polymerization temperature was 70° C.This gave 0.95 kg of polypropylene. The reactor has only very thindeposits on the interior wall and stirrer.

The catalyst activity was 125 kg PP/g metallocene·h. VN=392 cm³ /g;mp.=153° C.; M_(w) /M_(n) =2.6; the proportion extractable with heptaneis 4.1%.

EXAMPLE 7

A dry 24 dm³ reactor was flushed with propylene and charged with 12 dm³of liquid propylene. 30 cm³ of methylaluminoxane solution in toluene (40mmol Al) were then added and the mixture was stirred at 30° C. for 5minutes.

In parallel thereto, 2.0 mg of compound 3 were dissolved in 15 cm³ ofmethylaluminoxane solution in toluene (20 mmol Al) and reacted byallowing to stand for 5 minutes. The solution was then added to thereactor, heated (7° C./min) to the polymerization temperature of 70° C.by supply of heat and the polymerization system maintained at 70° C. for1 hour by means of cooling. The polymerization was stopped by additionof 10 standard dm³ of CO₂ gas. The excess monomer was vented, thepolymer was dried in vacuo. This gave 0.51 kg of polypropylene.

The catalyst activity was 255 kg PP/g metallocene×h.

VN=365 cm³ /g; mp.=154° C.;

II=97.5%; MFl (230/5)=2.8 dg/min;

M_(w) =517,599 g/mol, M_(w) /M_(n) =2.4.

EXAMPLE 8

The procedure of Example 7 was repeated, but the polymerizationtemperature was 50° C. The catalyst activity was 134 kg PP/gmetallocene×h.

VN=517 cm³ /g; mp.=159° C.;

II=98.4%; MFl (230/5)=0.9 dg/min;

M_(w) =786,500 g/mol, M_(w) /M_(n) =2.4.

EXAMPLE 9

The procedure of Example 7 was repeated, but the metallocene used wascompound 4.

The catalyst activity was 402 kg PP/g metallocene×h.

VN=142 cm³ /g; mp.=152° C.;

II=96.9%; MFl (230/5)=86 dg/min;

M_(w) =153,500 g/mol, M_(w) /M_(n) =2.0.

EXAMPLE 10

The procedure of Example 9 was repeated, but the polymerizationtemperature was 50° C. The catalyst activity was 176 kg PP/gmetallocene×h.

VN=237 cm³ /g; mp.=155° C.;

II=97.9%; MFl (230/5)=20 dg/min;

M_(w) =301,500 g/mol, M_(w) /M_(n) =2.7.

EXAMPLE 11

The procedure of Example 7 was repeated, but the metallocene used wascompound 4 and the polymerization temperature was 50° C.

The catalyst activity was 101 kg PP/g metallocene×h.

VN=476 cm³ /g; mp.=157° C.;

II=98%; MFl (230/5)=1.8 dg/min;

M_(w) =698,500 g/mol, M_(w) /M_(n) =5.8.

EXAMPLE 12

A dry 24 dm³ reactor was flushed with propylene and charged with 12standard dm³ of hydrogen and 12 dm³ of liquid propylene. 30 cm³ ofmethylaluminoxane solution in toluene (corresponding to 40 mmol Al) werethen added.

Parallel thereto, 2.5 mg of compound 3 were dissolved in 15 cm³ ofmethylaluminoxane solution in toluene (20 mmol Al) and preactivated byallowing to stand for 5 minutes.

The solution was then added to the reactor and, with the addition of 60g of ethylene, polymerization was carried out for 2 hours at 60° C. Themetallocene activity was 205 kg PP/g metallocene×h. The ethylene contentof the copolymer was 5.4% by weight.

VN=339 cm³ /g, M_(w) =384,000 g/mol, M_(w) /M_(n) =2.0, mp.=136° C.,according to NMR spectroscopy, the ethylene was predominantlyincorporated in an isolated form (random copolymer).

EXAMPLE 13

A dry 150 dm³ reactor was flushed with nitrogen and charged at 20° C.with 80 dm³ of a de-aromatized petroleum fraction having a boiling rangefrom 100 to 120° C. The gas space was then flushed free of nitrogen bypressurizing 5 times with 2 bar of propylene and depressurizing.

After addition of 50 l of liquid propylene, 75 cm³ of methylaluminoxanesolution in toluene (corresponding to 100 mmol Al) were added and thereactor contents were heated to 50° C. By metering in hydrogen, ahydrogen content of 2.0% was set in the gas space of the reactor andlater kept constant during the entire propylene copolymerization time bymetering in further amounts (on-line testing by gas chromatography).16.0 mg of compound 3 were dissolved in 37.5 ml of methylaluminoxanesolution in toluene (corresponding to 50 mmol Al) and added to thereactor after 15 minutes.

By means of cooling, the reactor was maintained at a polymerizationtemperature of 50° C. for 11 hours. After venting hydrogen and propyleneto a propylene pressure in the reactor of 1.0 bar and after addition of2.5 kg of ethylene, polymerization was continued for 5 hours at 50° C.The polymerization was then stopped by addition of 2 bar of CO₂ gas andthe polymer formed was separated off from the suspension medium on apressure filter. The product was dried for 24 hours at 80° C./200 mbar.This gave 17.5 kg of block copolymer powder, corresponding to ametallocene activity of 1093 kg PP/g metallocene×h.

VN=209 cm³ /g; M_(w) =217,500 g/mol; M_(w) /M_(n) =2.3; mp.=156° C.; MFl(230/5)=12 dg/min. The block copolymer contained 12.2% by weight ofethylene. Fractionation gave a content of 28.4% by weight ofethylene/propylene rubber. The glass transition temperature of therubber was -52° C.

EXAMPLE 14

Example 7 was repeated, but in addition 2.5 standard dm³ of hydrogenwere metered into the reactor prior to addition of the propylene. Themetallocene activity was 589 kg PP/g metallocene×h. VN=139 cm³ /g; M_(w)=149,500 g/mol, M_(w) /M_(n) =1.9; mp.=158° C.

EXAMPLE 15

A dry 16 dm³ reactor was flushed first with nitrogen and then withpropylene and charged with 10 dm³ of liquid propylene. 30 cm³ ofmethylaluminoxane solution in toluene were then added and the mixturewas stirred at 30° C. Parallel thereto, 3.0 mg of 5 were dissolved in 20cm³ of a methylaluminoxane solution in toluene (23 mmol Al) and reactedby allowing to stand for 15 minutes. The solution was then added to thereactor, heated (4° C./min) to the polymerization temperature of 50° C.by supply of heat and the polymerization system was maintained at 50° C.for 1 hour by means of cooling. The polymerization was stopped byaddition of 20 ml of isopropanol, the excess monomer was vented and thepolymer was dried in vacuo. This gave 0.56 kg of polypropylene. Thereactor had essentially no deposits on the interior wall and stirrer.

The catalyst activity was 189 kg PP/g metallocene·h; VN=449 cm³ /g;mp.=158° C.; M_(w) =529,500 g/mol; M_(w) /M_(n) =2.2.

EXAMPLE 16

The polymerization of Example 1 was repeated, except that 5.6 mg ofcompound 6 were used and the polymerization temperature was 70° C. Thisgave 0.17 kg of rubber-like polypropylene. The reactor had essentiallyno deposits on the interior wall and stirrer.

The catalyst activity was 30 kg PP/g metallocene·h; VN=80 cm³ /g;isotactic pentads (¹³ C-NMR)=58%.

EXAMPLES 17-22

Example 12 was repeated with higher amounts of comonomers. The resultsare listed in table 1 (random copolymers; copolymer rubber)

EXAMPLES 23-32

A dry 1.5 dm³ reactor was flushed with nitrogen and charged at 20° C.with 0.75 dm³ of a benzine, from which the aromatic components had beenremoved (Exxsol DSP 100/120). The gas space of the reactor was thenflushed free of nitrogen by injecting 2 bar of ethylen an decompressingthe reactor (5 times). 2.6 cm³ of a toluene solution ofmethylaluminoxane (3.5 mmol of Al, p=20) were then added. The reactorwas heated up to 30° C. (15 minutes) and at a stirring rate of 500 rpmthe desired monomer ratio of propylene and ethylene was established(partial pressures of propylene and ethylene see table 2). For theproduction of terpolymers 5-ethylidene-2-norbornene was additional addedto the polymerization system (amounts see table 2).

In parallel, 0.125 mg of metallocene 1 was dissolved in 1.25 cm³ of atoluene solution of methylaluminoxane (1.67 mmol of Al, p=20) and leftto stand for 5 minutes to achieve full reaction. The solution was theninjected into the reactor. The polymerization system was then heated upto 50° C. and kept at this temperature for one hour. The reaction wasterminated by addition of 2 ml of isopropanol.

Activities of the metallocene and product properties see table 2.

EXAMPLES 33-35

Example 3 was repeated, instead of metallocene 1 the metallocenes 7 (Ex.33), 8 (Ex. 34) and 9 (Ex. 35) were used. For results of thepolymerizations see table 3.

                                      TABLE 1                                     __________________________________________________________________________             example                                                                       12     17      18      19      20     21      22                     __________________________________________________________________________    comonomer                                                                              60 g ethylene                                                                        150 g ethylene                                                                        300 g ethylene                                                                        500 g ethylene                                                                        1 kg ethylene                                                                        100 g 1-hexene                                                                        100 g 4-methyl-                                                               1-pentene              met. activity                                                                          205    298     279     322     299    238     198                    [kg copolymer/g                                                               met × h]                                                                comonomer cont.                                                                        5.4    8.9     19.8    30      62.4   3.8     4.6                    [wt.-%]                                                                       i. copolymer                                                                  melting point                                                                          136    103     --      --      --     132     128                    [°C.]                                                                  glass transition                                                                       -10    -22     -38     -48     -50    -12     -11                    temperature                                                                   T.sub.g [°C.]                                                          __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________                   example                                                                       23 24  25  26  27  28  29  30  31  32                          __________________________________________________________________________    partial pressure                                                                             2.5                                                                              2   1   1   1   2   1   1   1   1                           propylene [bar]                                                               partial pressure ethylene [bar]                                                              -- 2   3   4   5   3   3   3   3   3                           5-ethylidene-2-norbornene [ml]                                                               -- --  --  --  --  --  1.25                                                                              2,5 5   10                          met. activity  80 118 159 149 201 121 102 138 96  89                          [kg polymer/g met × h]                                                  viscosity number                                                                             n.m.                                                                             129 132 120 114 104 69  58  63  65                          VN [cm.sup.3 /g]                                                              ethylene cont. [wt.-%]                                                                       -- 11.5                                                                              22  38  58  25  30  28  35  33                          in the polymer                                                                ethylidene-norbornene cont.                                                                  -- --  --  --  --  --  2.4 4.2 5.9 8.7                         [wt.-%] in the polymer                                                        glass transition temperature                                                                 n.m.                                                                             -25.4                                                                             -43.3                                                                             -47.5                                                                             -52.6                                                                             -40.6                                                                             -51 -51.6                                                                             -57.3                                                                             -59.8                       T.sub.g [°C.]                                                          __________________________________________________________________________

                  TABLE 3                                                         ______________________________________                                                    example                                                                       33        34     35                                               ______________________________________                                        met. activity 296         219    196                                          [kg PP/g met. × h]                                                      VN [cm.sup.3 /g]                                                                            54          294    269                                          melting point [°C.]                                                                  141         145    148                                          M.sub.w /M.sub.n                                                                            2.3         2.5    2.1                                          ______________________________________                                    

EXAMPLE 36

Use of a supported metallocene:

a) Preparation of the supported cocatalyst

The supported cocatalyst was prepared as described in EP 578 838 in thefollowing way in an explosion-proofed stainless-steel reactor fittedwith a 60 bar pump system, inert-gas supply, temperature control byjacket cooling and a second cooling circuit via a heat exchanger in thepump system. The pump system drew the contents out of the reactor via aconnector in the reactor through a riser pipe via a heat exchanger. Themixer was installed in such a way that a narrowed tube cross-section,where an increased flow rate occurred, was formed in the feed line, anda thin feed line through which--in cycles--in each case a defined amountof water under 40 bar of argon could be fed in run into its turbulencezone axially and against the flow direction. The reaction was monitoredvia a sampler in the pump circuit.

5 dm³ of decane were introduced under inert conditions into theabove-described reactor with a capacity of 16 dm³. 0.3 dm³ (=3.1 mol) oftrimethylaluminum were added at 25° C. 250 g of silica gel SD 3216-30(Grace AG) which had previously been dried at 120° C. in an argonfluidized bed were then metered into the reactor via a solids funnel andhomogeneously distributed with the aid of the stirrer and the pumpsystem. The total amount of 45.9 g of water was added to the reactor inportions of 0.1 cm³ every 15 seconds over the course of 2 hours. Thepressure, caused by the argon and the evolved gases, was kept constantat 10 bar by pressure-regulation valves. When all the water had beenintroduced, the pump system was switched off and the stirring wascontinued at 25° C. for a further 5 hours. The solvent was removed via apressure filter, and the cocatalyst solid was washed with decane andthen dried in vacuo. The isolated solid contains 18.7% by weight ofaluminum. 15 g of this solid (104 mmol of Al) were suspended in 100 cm³of this toluene in a stirrable vessel and cooled to -30° C. At the sametine, 200 mg of the metallocene 1 were dissolved in 75 cm³ of tolueneand added dropwise to the suspension over the course of 30 minutes. Themixture was slowly warmed to room temperature with stirring, duringwhich time the suspension took on a red color. The mixture wassubsequently stirred at 70° C. for 1 hour, cooled to room temperatureand filtered, and the solid was washed 3 times with 100 cm³ of toluenein each case and once with 100 cm³ of hexane. The hexane-moist filterresidue whick remained was dried in vacuo, giving 12.7 mg of zirconoceneper gram of catalyst.

b) Polymerization

1.0 g of the catalyst prepared under a) were suspended in 25 cm³ of abenzine fraction having the boiling range 100°-120° C. (Exxsol DSP100/120). In paralell, a dry 24 dm³ reactor was flushed first withnitrogen and subsequently with propylene and filled with 12 dm³ ofliquid propylene and with 1.5 dm³ of hydrogen. 3 cm³triisobutylaluminium (12 mmol) were then diluted with 30 ml of hexaneand introduced into the reactor, and the batch was stirred at 30 ° C.for 15 minutes. The catalyst suspension was subsequently introduced intothe reactor, and the polymerization system was heated to thepolymreization temperature of 70° C. (10° C./min), and kept at 70° C.for 1 hour by cooling. The polymerization was terminated by addition of20 ml of isopropanol. The excess monomer was removed as a gas, and thepoylmer was dried in vacuo, giving 2.4 kg of polypropylene powder.

Fractionation of the polymer by heptane extraction gave an heptanesoluble content of 0.9% by weight (VN=112 cm³ /g) and an insolublecontent of 99.1% by weight (VN=469 cm³ /g). The granules prepared inthis contained no fines<250 μm, the d₅₀ value was 980 μm (averageparticle size).

EXAMPLE 37

0.125 mg of metallocene 1 was solved in 1.25 ml MAO/toluene solution andmixed for 15 minutes. Meanwhile a stirred inert 1.5 dm³ reactor isfilled with 750 ml inert diesel oil (b.p. 100°-120° C.) and 3.75 mlMAO/toluene solution. The reactor is heated up to 70° C. and thepolymerization started by adding the catalyst solution at 750 rpm with 5bar ethylene. After 1 hour the reactor is decompressed, and the polymerfiltered off from the suspension, washed with acetone and dried for 12 hin a vacuum drying cabinet.

31 g polyethylen powder was recovered, corresponding to 248 kgPE/gmetallocene/h, with VN=520 cm³ /g. The polydispersity is M_(w) /M_(n)=2.7.

EXAMPLE 38

Example 37 was repeated with 0.125 mg of metallocene 2. 40.8 g PE wasrecovered, corresponding to 326 kgPE/g metallocene/h, with VN=720 cm³/g. M_(w) /M_(n) =2.8.

EXAMPLE 39

Example 37 was repeated with 0.5 bar hydrogen applied befor addition ofethylen. 35 g PE was recovered, with VN=75 cm³ /g. M_(w) /M_(n) =2.8.

EXAMPLE 40

Example 39 was repeated with 1 bar hydrogen insted of 0.5 bar. 28 g PEwax was recovered, with VN=22 cm³ /g. The melt viscosity at 140° C. was550 mPas. M_(w) /M_(n) =2.6

EXAMPLE 41

Example 37 was repeated with 0.4 mg of metallocene 7. 25.1 g PE wasrecovered, corresponding to 62 kgPE/g metallocene/h, with VN=340 cm³ /g.M_(w) /M_(n) =2.8.

EXAMPLE 42

Example 37 was repeated with 0.125 mg of metallocene 8. 24 g PE wasrecovered, corresponding to 192 kgPE/g metallocene/h, with VN=440 cm³/g. M_(w) /M_(n) =2.8.

EXAMPLE 43

Example 37 was repeated with 0.125 mg of metallocene 9. 30 g PE wasrecovered, corresponding to 240 kgPE/g metallocene/h, with VN=495 cm³/g. M_(w) /M_(n) =2.7.

EXAMPLE 44

Example 43 was repeated with additional 20 ml 1-hexene added togetherwith the diesel oil. The polymerization was stopped after 15 minutes byaddition of 0.5 bar CO₂. 9 g ethylene/1-hexene copolymer was recovered,corresponding to 288 kgPE/g metallocene/h, with VN=250 cm³ /g. 8.96 mol% hexene was found in copolymer by ¹³ C-NMR.

We claim:
 1. A polynuclear metallocene compound of the formula I##STR15## where M¹ are identical or different and are a metal of groupIVb, Vb or VIb of the Periodic Table,X are identical or different andare hydrogen, a C₁ -C₁₀ -alkyl group, a C₁ -C₁₀ -alkoxy group, a C₆ -C₁₀-aryl group, a C₆ -C₁₀ -aryloxy group, a C₂ -C₁₀ -alkenyl group, a C₇-C₄₀ -arylalkyl group, a C₇ -C₄₀ -alkylaryl group, a C₈ -C₄₀-aryl-alkenyl group, an OH group, a halogen atom or pseudohalogen, L andL' are identical or different and are π ligand or another electrondonor, k is 2 if B is ##STR16## and k is an integer ≧2 if B is ##STR17##where R¹ are identical or different and are a divalenthydrocarbon-containing bridge structure, the radicals R² are identicalor different and are a hydrogen atom, a halogen atom or ahydrocarbon-containing radical, R³ is a trivalent hydrocarbon-containingradical, and n is k and m is k-1 and M² is silicon, germanium or tin. 2.A polynuclear metallocene compound of the formula II ##STR18## where M¹are identical or different and are a metal of group IVb, Vb or VIb ofthe Periodic Table,X are identical or different and are hydrogen, a C₁-C₁₀ -alkyl group, a C₁ -C₁₀ -alkoxy group, a C₆ -C₁₀ -aryl group, a C₆-C₁₀ -aryloxy group, a C₂ -C₁₀ -alkenyl group, a C₇ -C₄₀ -arylalkylgroup, a C₇ -C₄₀ -alkylaryl group, a C₈ -C₄₀ -aryl-alkenyl group, an OHgroup, a halogen atom or pseudo-halogen, the radicals R⁵, R⁶, R⁷ and R⁸are identical or different and are a hydrogen atom, a halogen atom, a C₁-C₁₀ -alkyl group which can be halogenated, a C₆ -C₂₀ -aryl group, a C₇-C₄₀ -arylalkyl group, a C₇ -C₄₀ -alkylaryl group, a C₂ -C₁₀ -alkenylgroup, a C₈ -C₄₀ -arylalkenyl group, a --NR¹⁵ ₂, --SR¹⁵, --OSiR¹⁵ ₃,--SiR¹⁵ ₃ or --PR¹⁵ ₂ radical, where R¹⁵ is identical or different andis a C₁ -C₁₀ -alkyl group or a C₆ -C₁₀ -aryl group, or two or moreadjacent radicals R⁵, R⁶, R⁷ and R⁸ together with the atoms connectingthem form a ring system, R⁹ to R¹⁴ are identical or different and are ahydrogen atom, a halogen atom, a C₁ -C₁₀ -alkyl group which can behalogenated, a C₆ -C₂₀ -aryl group, a C₇ -C₄₀ -arylalkyl group, a C₇-C₄₀ -alkylaryl group, a C₂ -C₁₀ -alkenyl group, a C₈ -C₄₀ -arylalkenylgroup, a --NR¹⁵ ₂, --SR¹⁵, --OSiR¹⁵ ₃, --SiR¹⁵ ₃ or --PR¹⁵ ₂ radical,where R¹⁵ is identical or different and is a C₁ -C₁₀ -alkyl group or aC₆ -C₁₀ -aryl group, or two or more adjacent radicals R⁹, R¹⁰, R¹¹, R¹²,R¹³ and R¹⁴ together with the atoms connecting them form a ring system,k is 2, if B is ##STR19## and k is an integer ≧2, if B is ##STR20##where R¹ are identical or different and are a divalenthydrocarbon-containing C₁ -C₄₀ bridge structure, the radicals R² areidentical or different and are a hydrogen atom, a halogen atom or ahydrocarbon-containing C₁ -C₄₀ radical, R³ is a trivalenthydrocarbon-containing C₁ -C₄₀ radical, and n is k and m is k-1 and M²is silicon, germanium or tin.
 3. A polynuclear metallocene compound asclaimed in claim 2, wherein M¹ are identical or different and arezirconium or hafnium, the radicals X are identical and are a C₁ -C₄-alkyl group, a C₇ -C₁₀ -alkylaryl group or a halogen atom,R⁵ to R⁸ areidentical or different and are a hydrogen atom, a C₁ -C₁₀ -alkyl group,a C₆ -C₂₀ -aryl group or a SiR¹⁵ ₃ radical, where R¹⁵ is a C₁ -C₁₀-alkyl group, or the radicals R⁵ and R⁶ and/or R⁷ and R⁸ together withthe atoms connecting them form an aromatic or aliphatic ring system, R⁹to R¹⁴ are identical or different and are a hydrogen atom, a C₁ -C₁₀-alkyl group or a C₆ -C₂₀ -aryl group, or R⁹ and R¹⁰ and/or two or moreadjacent radicals R¹¹, R¹², R¹³ and R¹⁴ together with the atomsconnecting them form an aromatic or aliphatic ring system, k is 2, B is##STR21## where M² is silicon, R¹ are identical or different and are adivalent linear or branched C₁ -C₆ -alkyl group or C₂ -C₁₀ -alkenylgroup, and the radicals R² are identical or different and are hydrogen,a C₁ -C₄ -alkyl group or a C₆ -C₁₀ -aryl group.
 4. A process forpreparing a polynuclear metallocene compound as claimed in claim 1,which comprises deprotonating compounds LH and L'H with a base andreacting the deprotonated compounds with a reagent ##STR22## to give acompound of the formula A3 or one of its isomers ##STR23## andsubsequently deprotonating this with 2 k equivalents of a base andreacting the deprotonated compound with k equivalents of a metaltetrahalide to give the compound A4 ##STR24## and optionally reactingwith a derivatizing reagent to give a compound of the formula I and L,L¹, B, K, M¹, and X are defined in claim 1, HAL is a halogen and inwhich X is not halogen.
 5. The polynuclear metallocene compound asclaimed in claim 1, wherein the compound of formula 1 is selected fromthe group consisting of: 1.6-bis[methylsilyl(fluorenyl)(cyclopentadienyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl(indenyl)(cyclopentadienyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl(fluorenyl)(3-methylcyclopentadienyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl(indenyl)(3-methylcyclopentadienyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-(fluorenyl)(3-isopropylcyclopentadienyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-(indenyl)(3-isopropylcyclopentadienyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-(2-methylindenyl)(cyclopentadienyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(cyclopentadienyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-(4-phenylindenyl)(cyclopentadienyl)-zirconiumdichloride]hexane,1,6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-(fluorenyl)(3-phenylcyclopentadienyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-(indenyl)(3-phenylcyclopentadienyl)-zirconiumdichloride]hexane,1,6-bis[methylsilyl-(2-methyl-4,5-benzoindenyl)(cyclopentadienyl)zirconiumdichloride]hexane, 1.6-bis[methylsilyl-(2-methyl-4,6-diisopropylindenyl)(cyclopentadienyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-(2-methyl-4-(1-naphthylindenyl)-(cyclopentadienyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-(2-ethyl-4-phenylindenyl)(cyclopentadienyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-(2-methyl-4,5-benzoindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-(2-methyl-4,6-diisopropylindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-(2-methyl-4-(1-naphthylindenyl)-(2,3,5-trimethylcyciopentadienyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-(2-ethyl-4-phenylindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride]hexane,1,2-bis[methylsilyl-(fluorenyl)(cyclopentadienyl)-zirconiumdichloride]ethane,1,2-bis[methylsilyl-(indenyl)(cyclopentadienyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(fluorenyl)(3-methylcyclopenta-dienyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(indenyl)(3-methylcyclopentadienyl)-zirconiumdichloride]ethane,1,2-bis[methylsilyl-(fluorenyl)(3-isopropylcyclopentadienyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(indenyl)(3-isopropylcyclopentadienyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(2-methylindenyl)(cyclopentadienyl)-zirconiumdichloride]ethane, 1.2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(cyclopentadienyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(4-phenylindenyl)(cyclopentadienyl)-zirconiumdichloride]ethane,1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(fluorenyl)(3-phenylcyclopentadienyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(indenyl)(3-phenylcyclopentadienyl)-zirconiumdichloride]ethane,1,2-bis[methylsilyl-(2-methyl-4,5-benzoindenyl)(cyclopentadienyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(2-methyl-4,6-diisopropylindenyl)-(cyclopentadienyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(2-methyl-4-(1-naphthylindenyl)-(cyclopentadienyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(2-ethyl-4-phenylindenyl)(cyclopentadienyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(2-methyl-4,5-benzoindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(2-methyl-4,6-diisopropylindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride]-ethane,1,2-bis[methylsilyl-(2-methyl-4-(1-naphthylindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride]-ethane, 1.2-bis[methylsilyl-(2-ethyl-4-phenylindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride]ethane,1,4-disilacyclohexane-1,4-diylidene[(fluorenyl)(cyclopentadienyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(indenyl)(cyclopentadienyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(fluorenyl)(3-methylcyclopentadienyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(indenyl)(3-methylcyclopentadienyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(fluorenyl)(3-iso-propylcyclopentadienyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(indenyl)(3-iso-propylcyclopentadienyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(2-methylindenyl)(cyclopentadienyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenylindenyl)(cyclopentadienyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(4-phenylindenyl)(cyclopentadienyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenyloindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(fluorenyl)(3-phenylcyclopentadienyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(indenyl)(3-phenylcyclopentadienyl)zirconiumdichloride], 1.4-disilacyclohexane-1,4-diylidene[(2-methyl-4,5-benzoindenyl)(cyclopentadienyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4,6-diisopropylindenyl)(cyclopentadienyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-(1-napthylindenyl)(cyclopentadienyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(2-ethyl-4-phenylindenyl)(cyclopentadienyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4,5-benzo-indenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4,6-diiso-propylindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-(1-naphthylindenyl)(2,3,5-trimethylcyclopentadienyl)-zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(2-ethyl-4-phenyl-indenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(fluorenyl)(cyclopentadienyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(indenyl)(cyclopentadienyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene-[(fluorenyl)(3-methylcyclopentadienyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(indenyl)(3-methylcyclopentadienyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene-[(fluorenyl)(3-isopropylcyclopentadienyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene-[(indenyl)(3-isopropylcyclopentadienyl)zirconiumdichloride], 9.10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)zirconiumdichloride],9,10-dihydro-9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methylindenyl)(cyclopentadienyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-phenylindenyl)(cyclopentadienyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(4-phenylindenyl)(cyclopentadienyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-phenylindenyl)(2,3,5-trimethylcyclopentadienyl)-zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(fluorenyl)(3-phenylcyclopentadienyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(indenyl)(3-phenylcyclopentadienyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4,5-benziondenyl)(cyclopentadienyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4,6-diisopropylindenyl)(cyclopentadienyl)-zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-(1-naphthylindenyl)cyclopentadienyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2ethyl-4-phenylindenyl)(cyclopentadienyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4,5-benzoindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4,6-diisopropylindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-(1-naphthylindenyl)(2,3,5-trimethylcyclopentadienyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-ethyl-4-phenylindenyl)(2,3,5-trimethylcyclopentadienyl)-zirconiumdichloride],
 1. 6-bis[methylsilyl-bis(indenyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-bis(2-methylindenyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-bis(2-methyl-4,5-benzoindenyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-bis(2-methyl-4-(1-naphthyl)indenyl)-zirconiumdichloride]hexane,1,6-bis[methylsilyl-bis(2-methyl-4-isopropylindenyl)-zirconiumdichloride]hexane,1,6-bis[methylsilyl-bis(2-methyl-4,6-diisopropylindenyl)-zirconiumdichloride]hexane, 1,6-bis[methylsilyl-bis(2-ethylindenyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-bis(2-ethyl-4-phenylindenyl)-zirconiumdichloride]hexane,1,6-bis[methylsilyl-bis(2-ethyl-4-(1-naphthyl)indenyl)-zirconiumdichloride]hexane,1,6-bis[methylsilyl-bis(2-ethyl-α-acenaphthindenyl)-zirconiumdichloride]hexane, 1,2-bis[methylsilyl-bis(indenyl)zirconiumdichloride]ethane, 1,2-bis[methylsilyl-bis(2-methylindenyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-bis(2-methyl-4,5-benzoindenyl)-zirconiumdichloride]ethane,1,2-bis[methylsilyl-bis(2-methyl-4-(1-naphthyl)indenyl)-zirconiumdichloride]ethane,1,2-bis[methylsilyl-bis(2-methyl-4-isopropylindenyl)-zirconiumdichloride]ethane,1,2-bis[methylsilyl-bis(2-methyl-4,6-diisopropylindenyl)-zirconiumdichloride]ethane, 1,2-bis[methyslilyl-bis(2-ethylindenyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-bis(2-ethyl-4-phenylindenyl)-zirconiumdichloride]ethane,1,2-bis[methylsilyl-bis(2-ethyl-4-naphthyl)indenyl)-zirconiumdichloride]ethane,1,2-bis[methylsilyl-bis(2-ethyl-α-acenaphthinedenyl)-zirconiumdichloride]ethane,
 1. 2-bis[ethylsilyl-bis(indenyl)zirconiumdichloride]ethane,1,2-bis[ethylsilyl-bis(2-methylindenyl)zirconiumdichloride]ethane,1,2-bis[ethylsilyl-bis(2-methyl-4-phenylindenyl)-zirconiumdichloride]ethane,1,2-bis[ethylsilyl-bis(2-methyl-4,5-benzoindenyl)-zirconiumdichloride]ethane,1,2-bis[ethylsilyl-bis(2-methyl-4-(1-naphthyl)indenyl)-zirconiumdichloride]ethane,1,2-bis[ethylsilyl-bis(2-methyl-4-isopropylindenyl)-zirconiumdichloride]ethane,1,2-bis[ethylsilyl-bis(2-methyl-4,6-diisopropylindenyl)-zirconiumdichloride]ethane, 1,2-bis[ethylsilyl-bis(2-ethylindenyl)zirconiumdichloride]ethane,1,2-bis[ethylsilyl-bis(2-ethyl-4-phenylindenyl)zirconiumdichloride]ethane,1,2-bis[ethylsilyl-bis(2-ethyl-4-(1-naphthyl)indenyl)-zirconiumdichloride]ethane,1,2-bis[ethylsilyl-bis(2-ethyl-α-acenaphthindenyl)-zirconiumdichloride]ethane, 1,6-bis[ethylsilyl-bis(indenyl)zirconiumdichloride]hexane, 1,6-bis[ethylsilyl-bis(2-methylindenyl)zirconiumdichloride]hexane,1,6-bis[ethylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdichloride]hexane,1,6-bis[ethylsilyl-bis(2-methyl-4,5-benzoindenyl)zirconiumdichloride]hexane,1,6-bis[ethylsilyl-bis(2-methyl-4-(1-naphthyl)indenyl)-zirconiumdichloride]hexane,1,6-bis[ethylsilyl-bis(2-methyl-2-isopropylindenyl)zirconiumdichloride]hexane,1,6-bis[ethylsilyl-bis(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride]hexane, 1,6-bis[ethylsilyl-bis(2-ethylindenyl)zirconiumdichloride]hexane,1,6-bis[ethylsilyl-bis(2-ethyl-4-phenylindenyl)zirconiumdichloride]hexane,1,6-bis[ethylsilyl-bis(2-ethyl-4-(1-naphthyl)indenyl)zirconiumdichloride]hexane,1,6-bis[ethylsilyl-bis(2-ethyl-α-acenaphthindenyl)zirconiumdichloride]hexane,
 1. 3-bis[methylsilyl-bis(indenyl)zirconiumdichloride]-propane,1,3-bis[methlsilyl-bis(2-methylindenyl)zirconiumdichloride]propane,1,3-bis[methylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdichloride]propane,1,3-bis[methylsilyl-bis(2-methyl-4,5-benzoindenyl)zirconiumdichloride]propane,1,3-bis[methylsilyl-bis(2-methyl-4-(1-naphthyl)indenyl)-zirconiumdichloride]propane,1,3-bis[methylsilyl-bis(2-methyl-4-isopropylindenyl)zirconiumdichloride]propane,1,3-bis[methylsilyl-bis(2-methyl-4,6-diisopropylindenyl)-zirconiumdichloride]propane, 1,3-bis[methylsilyl-bis(2-ethylindenyl)zirconiumdichloride]propane,1,3-bis[methylsilyl-bis(2-ethyl-4-phenylindenyl)zirconiumdichloride]propane,1,3-bis[methylsilyl-bis(2-ethyl-4-(1-naphthyl)indenyl)zirconiumdichloride]propane,1,3-bis[methylsilyl-bis(2-ethyl-α-acenaphthindenyl)zirconiumdichloride]propane,1,4-disilacyclohexane-1,4-diylidene[bis(indenyl)zirconium dichloride],1,4-disilacyclohexane-1,4-diylidene[bis(2-methylindenyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[bis(2-ethylindenyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[bis(2-methyl-4-phenylindenyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[bis(2-methyl-4-(1-naphthylindenyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[bis(2-methyl-4-isopropylindenyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[bis(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[bis(2-methyl-4,5-benzoindenyl)zirconiumdichloride], 1.4-disilacyclohexane-1,4-diylidene[bis(2-ethyl-4-phenyl-indenyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[bis(2-methyl-α-acenaphthindenyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[bis(indenyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[bis(2-methylindenyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[bis(2-ethylindenyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[bis(2-methyl-4-phenylindenyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[bis(2-methyl-4-(1-naphthylindenyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[bis(2-methyl-4-isopropylindenyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[bis(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[bis(2-methyl-4,5-benzoindenyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[bis(2-ethyl-4-phenylindenyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[bis(2-methyl-α-acenaphthindenyl)zirconiumdichloride], 1.4-dihydro-1,4-disilabenzene-1,4-diylidene[bis(indenyl)zirconiumdichloride],1,4-dihydro-1,4-disilabenzene-1,4-diylidene[bis(2-methyl-indenyl)zirconiumdichloride],1,4-dihydro-1,4-disilabenzene-1,4-diylidene[bis(2-ethyl-indenyl)zirconiumdichloride],1,4-dihydro-1,4-disilabenzene-1,4-diylidene[bis(2-methyl-4-phenylindenyl)zirconiumdichloride],1,4-dihydro-1,4-disilabenzene-1,4-diylidene[bis(2-methyl-4-(1-naphthylindenyl)zirconiumdichloride],1,4-dihydro-1,4-disilabenzene-1,4-diylidene[bis(2-methyl-4-isopropylindenyl)zirconiumdichloride],1,4-dihydro-1,4-disilabenzene-1,4-diylidene[bis(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride],1,4-dihydro-1,4-disilabenzene-1,4-diylidene[bis(2-methyl-4,5-benzoindenyl)zirconiumdichloride],1,4-dihydro-1,4-disilabenzene-1,4-diylidene[bis(2-ethyl-4-phenylindenyl)zirconiumdichloride],1,4-dihydro-1,4-disilabenzene-1,4-diylidene[bis(2-methyl-α-acenaphthindenyl)zirconiumdichloride],1,4-dihydro-1,4-disila-2,3,5,6-tetraphenylbenzene-1,4-diylidene[bis(indenyl)zirconiumdichloride],1,4-dihydro-1,4-disila-2,3,5,6-tetraphenylbenzene-1,4-diylidene[bis(2-methylindenyl)zirconiumdichloride],1,4-dihydro-1,4-disila-2,3,5,6-tetraphenylbenzene-1,4-diylidene[bis(2-ethylindenyl)zirconiumdichloride], 1.4-dihydro-1,4-disila-2,3,5,6-tetraphenylbenzene-1,4-diylidene[bis(2-methyl-4-phenylindenyl)zirconiumdichloride],1,4-dihydro-1,4-disila-2,3,5,6-tetraphenylbenzene-1,4-diylidene[bis(2-methyl-4-(1-naphthylindenyl)zirconiumdichloride],1,4-dihydro-1,4-disila-2,3,5,6-tetraphenylbenzene-1,4-diylidene[bis(2-methyl-4-isopropylindenyl)zirconiumdichloride],1,4-dihydro-1,4-disila-2,3,5,6-tetraphenylbenzene-1,4-diylidene[bis(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride],1,4-dihydro-1,4-disila-2,3,5,6-tetraphenylbenzene-1,4-diylidene[bis(2-methyl-4,5-benzoindenyl)zirconiumdichloride],1,4-dihydro-1,4-disila-2,3,5,6-tetraphenylbenzene-1,4-diylidene[bis(2-ethyl-4-phenylindenyl)zirconiumdichloride],1,4-dihydro-1,4-disila-2,3,5,6-tetraphenylbenzene-1,4-diylidene[bis(2-methyl-α-acenaphthindenyl)zirconiumdichloride],1,6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methylindenyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(indenyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-4,5-benzoindenyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-4-(1-naphthyl)indenyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-4-isopropylindenyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride]hexane, 1.6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-ethyl-indenyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-ethyl-4-phenylindenyl)zirconiumdichloride]hexane,1,6-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-α-acenaphthindenyl)zirconiumdichloride]hexane,1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(indenyl)-zirconiumdichloride]ethane,1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-indenyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-4,5-benxoindenyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-4,5-benxoindenyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-4-(1-naphthyl)indenyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-4-isopropylindenyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-methyl-4-phenylindenyl)(2-ethyl-indenyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-ethyl-4-phenylindenyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-ethyl-4-(1-naphthyl)indenyl)zirconiumdichloride]ethane,1,2-bis[methylsilyl-(2-methyl-4-phenylindenyl)(2-α-acenaphthindenyl)zirconiumdichloride]ethane, 1.4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenylindenyl)(indenyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methylindenyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-ethylindenyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4-(1-naphthylindenyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4-isopropylindenyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4,5-benzoindenyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4-phenylindenyl)zirconiumdichloride],1,4-disilacyclohexane-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-.alpha.-methylacenaphthindenyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-phenylindenyl)(indenyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-phenylindenyl)(2-methylindenyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-phenylindenyl)(2-ethylindenyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4-isopropylindenyl)zirconiumdichloride], 9.10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4,5-benzoindenyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-phenylindenyl)(2-ethyl-4-phenylindenyl)zirconiumdichloride],9,10-dihydro-9,10-disilaanthracene-9,10-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-α-acenaphthindenyl)zirconiumdichloride],1,4-dihydro-1,4-disilabenzene-1,4-diylidene[(2-methyl-4-phenylindenyl)(indenyl)zirconiumdichloride],1,4-dihydro-1,4-disilabenzene-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methylindenyl)zirconiumdichloride],1,4-dihydro-1,4-disilabenzene-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-ethylindenyl)zirconiumdichloride],1,4-dihydro-1,4-disilabenzene-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4-(1-naphthylindenyl)zirconiumdichloride],1,4-dihydro-1,4-disilabenzene-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4-isopropylindenyl)zirconiumdichloride],1,4-dihydro-1,4-disilabenzene-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride],1,4-dihydro-1,4-disilabenzene-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-4,5-benzoindenyl)zirconiumdichloride],1,4-dihydro-1,4-disilabenzene-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-ethyl-4-phenylindenyl)zirconiumdichloride] and1,4-dihydro-1,4-disilabenzene-1,4-diylidene[(2-methyl-4-phenylindenyl)(2-methyl-α-acenaphthindenyl)zirconiumdichloride].
 6. The polynuclear metallocene compound as claimed in claim3, wherein R¹ is identical or different and in 1,2-ethylene,1,3-propylene, 1,4-butylene or 1,6-hexylene.